EP0532943A1 - Polyester resin - Google Patents
Polyester resin Download PDFInfo
- Publication number
- EP0532943A1 EP0532943A1 EP92114522A EP92114522A EP0532943A1 EP 0532943 A1 EP0532943 A1 EP 0532943A1 EP 92114522 A EP92114522 A EP 92114522A EP 92114522 A EP92114522 A EP 92114522A EP 0532943 A1 EP0532943 A1 EP 0532943A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polyester resin
- mole
- film
- ethylene oxide
- oxide adduct
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001225 polyester resin Polymers 0.000 title claims abstract description 160
- 239000004645 polyester resin Substances 0.000 title claims abstract description 160
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 286
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims abstract description 93
- -1 bisphenol compound Chemical class 0.000 claims abstract description 66
- 229920005989 resin Polymers 0.000 claims abstract description 35
- 239000011347 resin Substances 0.000 claims abstract description 35
- 150000002009 diols Chemical class 0.000 claims abstract description 31
- 150000002148 esters Chemical class 0.000 claims abstract description 30
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229930185605 Bisphenol Natural products 0.000 claims abstract description 22
- 238000000071 blow moulding Methods 0.000 claims abstract description 14
- 238000000465 moulding Methods 0.000 claims abstract description 13
- 125000003118 aryl group Chemical group 0.000 claims abstract description 8
- 238000001125 extrusion Methods 0.000 claims abstract description 6
- 238000001746 injection moulding Methods 0.000 claims abstract description 4
- 239000002253 acid Substances 0.000 claims description 115
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims description 109
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 105
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 claims description 94
- 229920006267 polyester film Polymers 0.000 claims description 73
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 32
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical group OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 26
- 229920001223 polyethylene glycol Polymers 0.000 claims description 19
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims description 17
- 230000000977 initiatory effect Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- ARCGXLSVLAOJQL-UHFFFAOYSA-N trimellitic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C(C(O)=O)=C1 ARCGXLSVLAOJQL-UHFFFAOYSA-N 0.000 claims description 12
- 150000005846 sugar alcohols Polymers 0.000 claims description 11
- VPWNQTHUCYMVMZ-UHFFFAOYSA-N 4,4'-sulfonyldiphenol Chemical compound C1=CC(O)=CC=C1S(=O)(=O)C1=CC=C(O)C=C1 VPWNQTHUCYMVMZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000007654 immersion Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 claims description 6
- CYIDZMCFTVVTJO-UHFFFAOYSA-N pyromellitic acid Chemical compound OC(=O)C1=CC(C(O)=O)=C(C(O)=O)C=C1C(O)=O CYIDZMCFTVVTJO-UHFFFAOYSA-N 0.000 claims description 6
- 229920000728 polyester Polymers 0.000 claims description 4
- 150000008064 anhydrides Chemical class 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 3
- 125000003827 glycol group Chemical group 0.000 claims description 2
- 239000012778 molding material Substances 0.000 abstract description 5
- 238000006243 chemical reaction Methods 0.000 description 77
- 238000006116 polymerization reaction Methods 0.000 description 70
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 66
- 239000002685 polymerization catalyst Substances 0.000 description 44
- 239000003381 stabilizer Substances 0.000 description 38
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 description 37
- 229920000642 polymer Polymers 0.000 description 32
- 238000011156 evaluation Methods 0.000 description 31
- 238000005259 measurement Methods 0.000 description 31
- 230000000052 comparative effect Effects 0.000 description 30
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 27
- 238000005809 transesterification reaction Methods 0.000 description 27
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 24
- WOZVHXUHUFLZGK-UHFFFAOYSA-N dimethyl terephthalate Chemical compound COC(=O)C1=CC=C(C(=O)OC)C=C1 WOZVHXUHUFLZGK-UHFFFAOYSA-N 0.000 description 22
- 229920006257 Heat-shrinkable film Polymers 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000003054 catalyst Substances 0.000 description 14
- 239000011342 resin composition Substances 0.000 description 14
- CXMXRPHRNRROMY-UHFFFAOYSA-N sebacic acid Chemical compound OC(=O)CCCCCCCCC(O)=O CXMXRPHRNRROMY-UHFFFAOYSA-N 0.000 description 14
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 12
- 229940119177 germanium dioxide Drugs 0.000 description 12
- 239000004246 zinc acetate Substances 0.000 description 12
- 238000010438 heat treatment Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- ORLQHILJRHBSAY-UHFFFAOYSA-N [1-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1(CO)CCCCC1 ORLQHILJRHBSAY-UHFFFAOYSA-N 0.000 description 6
- 230000032050 esterification Effects 0.000 description 6
- 238000005886 esterification reaction Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- BJZYYSAMLOBSDY-QMMMGPOBSA-N (2s)-2-butoxybutan-1-ol Chemical compound CCCCO[C@@H](CC)CO BJZYYSAMLOBSDY-QMMMGPOBSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 239000001361 adipic acid Substances 0.000 description 4
- 235000011037 adipic acid Nutrition 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 4
- BDJRBEYXGGNYIS-UHFFFAOYSA-N nonanedioic acid Chemical compound OC(=O)CCCCCCCC(O)=O BDJRBEYXGGNYIS-UHFFFAOYSA-N 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 3
- 239000004793 Polystyrene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 3
- 229920001577 copolymer Polymers 0.000 description 3
- 230000001627 detrimental effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 229920003207 poly(ethylene-2,6-naphthalate) Polymers 0.000 description 3
- 239000011112 polyethylene naphthalate Substances 0.000 description 3
- 229920000098 polyolefin Polymers 0.000 description 3
- 229920002223 polystyrene Polymers 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000002087 whitening effect Effects 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- 241000251468 Actinopterygii Species 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 229920006038 crystalline resin Polymers 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 125000001142 dicarboxylic acid group Chemical group 0.000 description 2
- IPZJQDSFZGZEOY-UHFFFAOYSA-N dimethylmethylene Chemical compound C[C]C IPZJQDSFZGZEOY-UHFFFAOYSA-N 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- 238000010348 incorporation Methods 0.000 description 2
- 229940071125 manganese acetate Drugs 0.000 description 2
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- KYTZHLUVELPASH-UHFFFAOYSA-N naphthalene-1,2-dicarboxylic acid Chemical compound C1=CC=CC2=C(C(O)=O)C(C(=O)O)=CC=C21 KYTZHLUVELPASH-UHFFFAOYSA-N 0.000 description 2
- RXOHFPCZGPKIRD-UHFFFAOYSA-N naphthalene-2,6-dicarboxylic acid Chemical class C1=C(C(O)=O)C=CC2=CC(C(=O)O)=CC=C21 RXOHFPCZGPKIRD-UHFFFAOYSA-N 0.000 description 2
- YCWSUKQGVSGXJO-NTUHNPAUSA-N nifuroxazide Chemical group C1=CC(O)=CC=C1C(=O)N\N=C\C1=CC=C([N+]([O-])=O)O1 YCWSUKQGVSGXJO-NTUHNPAUSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002985 plastic film Substances 0.000 description 2
- 229920006255 plastic film Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulfur dioxide Inorganic materials O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 description 1
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 description 1
- OTSZYGOOKXGLED-UHFFFAOYSA-N 1-methoxycarbonylnaphthalene-2-carboxylic acid Chemical compound C1=CC=C2C(C(=O)OC)=C(C(O)=O)C=CC2=C1 OTSZYGOOKXGLED-UHFFFAOYSA-N 0.000 description 1
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- YIMQCDZDWXUDCA-UHFFFAOYSA-N [4-(hydroxymethyl)cyclohexyl]methanol Chemical compound OCC1CCC(CO)CC1 YIMQCDZDWXUDCA-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- JGFBRKRYDCGYKD-UHFFFAOYSA-N dibutyl(oxo)tin Chemical compound CCCC[Sn](=O)CCCC JGFBRKRYDCGYKD-UHFFFAOYSA-N 0.000 description 1
- VNGOYPQMJFJDLV-UHFFFAOYSA-N dimethyl benzene-1,3-dicarboxylate Chemical compound COC(=O)C1=CC=CC(C(=O)OC)=C1 VNGOYPQMJFJDLV-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- UEGPKNKPLBYCNK-UHFFFAOYSA-L magnesium acetate Chemical compound [Mg+2].CC([O-])=O.CC([O-])=O UEGPKNKPLBYCNK-UHFFFAOYSA-L 0.000 description 1
- 239000011654 magnesium acetate Substances 0.000 description 1
- 229940069446 magnesium acetate Drugs 0.000 description 1
- 235000011285 magnesium acetate Nutrition 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920001707 polybutylene terephthalate Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 150000003503 terephthalic acid derivatives Chemical class 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- SRPWOOOHEPICQU-UHFFFAOYSA-N trimellitic anhydride Chemical compound OC(=O)C1=CC=C2C(=O)OC(=O)C2=C1 SRPWOOOHEPICQU-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229960000314 zinc acetate Drugs 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/672—Dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
Definitions
- the present invention relates to a polyester resin for use as a molding material for various moldings such as extrusion molding, blow molding, vacuum molding and injection molding, and particularly to a polyester resin suitable for use as a heat shrinkable polyester film for various packaging materials etc. and a bottle for direct blow molding. More particularly, the present invention is concerned with a polyester resin that can be used as a molding material, such as a bottle for direct blow molding, capable of improving crystallinity and, at the same time, moldability and oxidation stability without detriment to mechanical properties of polyethylene terephthalate and can also be used as a highly shrinkable polyester film having high shrinkage in a relatively low temperature region and excellent heat shrinking properties, such as less liability to uneven shrinkage.
- a heat shrinkable plastic film has been used for display, protection, binding, improvement in the added value of goods, etc. in the fields of containers, fishing rods, capacitors, rod-shaped fluorescent lamps, etc. and also for multipack and contact packaging for books, notebooks, etc.
- the development of various applications utilizing the shrinkability and shrinkage stress of the heat shrinkable film is anticipated in many fields other than those described above.
- Resins such as polyvinyl chloride, polystyrene and polyolefin have hitherto been used as a material for a heat shrinkable plastic film. These resins, however, have had problems with heat resistance, weather resistance, chemical resistance, etc.
- a polyvinyl chloride film is a heat shrinkable film having various shrinking properties. This film, however, is liable to experience the frequent occurrence of fish eye, and goods, wherein the above film subjected to printing is used as a packing material, have a spoiled appearance and a lower value. In order to obtain a heat shrinkable film free from fish eye, it is necessary to conduct excessive quality control, so problems occur such as a significant increase in the production cost of a film.
- the polyvinyl chloride is disadvantageous also in that incineration at the time of disposal results in a pollution problem, additives such as a plasticizer in polyvinyl chloride bleed out with the elapse of time to cause staining due to deposition of dust etc. and they are unsafe.
- the solvent resistance is so low that a special ink should be used for printing.
- spontaneous shrinkage occurs even at room temperature, the film should be stored in a cold place. Further, it also had a problem with disposal. Specifically, since incineration at a high temperature is necessary, large amounts of black smoke and an offensive smell are unfavorably generated at the time of the incineration.
- a polyester film is greatly expected as a material capable of solving the above-described problems, and the amount of use thereof has increased.
- the conventional heat shrinkable polyester film use was made of a copolymer polyester resin comprising a dicarboxylic acid moiety composed mainly of terephthalic acid and a diol moiety composed mainly of ethylene glycol and, copolymerized with the dicarboxylic acid moiety, isophthalic acid, sebacic acid, adipic acid or neopentyl glycol.
- the conventional heat shrinkable polyester film however, had no satisfactory heat shrinking properties. In particular, uneven shrinkage is liable to occur during shrinkage. For this reason, when the film covers a container, such as a bottle, and then shrunk, there occurs a problem in that letters or patterns printed on the film are distorted and the adhesion of the film to the container is unsatisfactory.
- the polyester film is inferior regarding shrinkability at a low temperature and therefore should be shrunk at a high temperature in order to attain the necessary degree of shrinkage, which gives rise to such problems as deformation and bottle whitening etc.
- the polyester film is used as a label for a polyethylene bottle, since the polyethylene bottle, as such, is inferior to a PET bottle etc. in heat resistance, the shrinking operation should be conducted at the relatively low temperature of about 70°C. For this reason, the development of a heat shrinkable film having excellent shrinking properties at a low temperature has been desired in the art.
- a heat shrinkable film comprising a copolymer polyester
- an ethylene oxide adduct of a bisphenol compound or an ethylene oxide adduct of a bisphenol derivative is used as a comonomer component and the retention time of residual stress at the time of the heat treatment is prolonged so as to improve the shrinking properties.
- Polyethylene terephthalate, polybutylene terephthalate, etc. have generally been used as a polyester resin for a molding material used in direct blow molding or the like. Further, modified polyester resins comprising said resins copolymerized with various monomers, such as isophthalic acid or cyclohexanedimethanol, polyethylene naphthalate comprising an acid moiety composed mainly of naphthalenedicarboxylic acid, etc. have been developed.
- the mechanical strength properties such as impact strength
- the melt viscosity of the resin is so low that it is very difficult to conduct molding, a comparison cannot be formed, and in particular, a large container cannot be molded.
- the modified polyester resin copolymerized with cyclohexanedimethanol is unsatisfactory although an improvement in moldability can be attained over that of a resin copolymerized with isophthalic acid.
- the heat stability of the resin is so poor that when the resin stays within a molding machine for a long period of time, the deterioration of the resin is significant.
- Polyethylene naphthalate has the feature that it has a higher melting point than the conventional polyester resins, but, it is unsatisfactory as a resin for a molding material with respect to mechanical properties and moldability.
- diethylene glycol produced as a by-product is contained in the resin, which leads to a lowering in the moldability and oxidation stability of the resin.
- An attempt to reduce the diethylene glycol content has been made by the addition of sodium hydroxide or the like during polymerization. Even a polyester resin produced by this method is unsatisfactory with respect to the moldability or oxidation stability although it is possible to reduce the diethylene glycol content to about 1.5% by weight.
- the present invention provides first a polyester resin comprising units of a dicarboxylic acid component composed mainly of an aromatic dicarboxylic acid or its ester forming derivative and a diol component composed mainly of ethylene glycol and an ethylene oxide adduct of a bisphenol compound or its derivative; the content of the ethylene oxide adduct of a bisphenol compound or its derivative being 0.1 to 50% by mole based on the whole diol component, and said resin further comprising 0.1 to 20% by weight of units of polyoxytetramethylene glycol and/or polyethylene glycol.
- the invention also provides a polyester resin comprising units of a dicarboxylic and component composed mainly of an aromatic dicarboxylic acid or its ester forming derivative and a diol component composed mainly of ethylene glycol and an ethylene oxide adduct of a bisphenol compound or its derivative; the content of the ethylene oxide adduct of a bisphenol compound or its derivative being 0.1 to 50% by mole based on the whole diol component, and said resin further comprising units of a tricarboxylic or higher polycarboxylic acid and/or a trihydric or higher polyhydric alcohol.
- the invention also provides a polyester resin comprising units of an acid component composed mainly of terephthalic acid or its ester forming derivative and a diol component composed mainly of ethylene glycol and an ethylene oxide adduct of bisphenol A; the content of the ethylene oxide adduct of bisphenol A being 3 to 98% by mole based on the whole diol component, and said polyester resin having an intrinsic viscosity of 0.5 to 1.4 dl/g and a diethylene glycol unit content of 1.2% by weight or less.
- the polyester resin of the present invention comprises units of a dicarboxylic acid component composed mainly of an aromatic dicarboxylic acid or its ester forming derivative and a diol component composed mainly of ethylene glycol and an ethylene oxide adduct of a bisphenol compound or its derivative.
- polyester resins according to the first and second inventions will now be described.
- aromatic dicarboxylic acid as a main component of the dicarboxylic acid component constituting the polyester resins according to the first and second inventions include terephthalic acid, isophthalic acid and naphthalene-1,4- and naphthalene-2,6-dicarboxylic acids.
- ester forming derivatives thereof include derivatives such as dialkyl esters and diaryl esters.
- the content of these aromatic dicarboxylic acids or their ester forming derivatives in the dicarboxylic acid component is preferably 80% by mole or more, still preferably 85% by mole or more, and when the content of the aromatic dicarboxylic acid or its ester forming derivative is less than 80% by mole, there is a tendency, when it is formed into, for example, a film, to lower the mechanical strength of the polyester film.
- the dicarboxylic acid component preferably includes terephthalic acid and isophthalic acid or their ester forming derivative.
- the content of the isophthalic acid or its ester forming derivative based on the whole dicarboxylic acid component is in the range of from 7 to 30% by mole, preferably in the range of from 10 to 30% by mole, still preferably in the range of from 12 to 30% by mole, because when the polyester resin is used as a heat shrinkable label for a container such as a bottle, the heat shrinkable film is used after the ends of the film are solvent-bonded to each other with a solvent, such as tetrahydrofuran, so as render the film in tubular form.
- the label is unfavorably peeled off.
- the content of isophthalic acid or its ester forming derivative was limited to the above-described range for the purpose of imparting a sufficient solvent-bonding property to the film, and when the content is less than 7% by mole, no sufficient improvement in the solvent-bonding property can be attained. On the other hand, when the content exceeds 30% by mole, shrinking properties, such as uneven and high percentage shrinkage become poor.
- aliphatic dicarboxylic acids or their ester forming derivatives other than those described above may be incorporated in an amount of less than 20% by mole, preferably less than 15% by mole for the purpose of enhancing the effect of the present invention.
- these aliphatic dicarboxylic acids are incorporated in an amount of 20% by mole or more, there is a possibility that when the polyester resin is formed into a film, the mechanical properties of the film are lowered.
- Examples of the aliphatic dicarboxylic acid useable in the present invention include glutaric acid, adipic acid, sebacic acid, azelaic acid, oxalic acid and succinic acid, and when the polyester resin is used as a heat shrinkable film, the incorporation of these aliphatic dicarboxylic acids or their ester forming derivatives in a suitable amount contributes to the enhancement of the percentage heat shrinkage.
- the diol component constituting the polyester resin according to the first and second inventions should be composed mainly of ethylene glycol and an ethylene oxide adduct of a bisphenol compound or its derivative, and the content of the ethylene oxide adduct of the bisphenol compound or its derivative should be in the range of from 0.1 to 50% by mole, preferably in the range of from 0.5 to 30% by mole based on the whole diol component, because when the polyester resin is used as a heat shrinkable film, if the content of the ethylene oxide adduct of bisphenol A is less than 0.1% by mole, no effect of reducing the uneven shrinkage can be attained, while if the content exceeds 50% by mole, shrinkage at a low temperature is lowered.
- Examples of the ethylene oxide adduct of the bisphenol compound or its derivative include those having structures represented by the following general formulae (1) and (2).
- X stands for CH2, C(CH3)2, C(CF3)2, O, S or SO2 and n and m are each a number satisfying a requirement represented by the formula 2 ⁇ n + m ⁇ 6.
- X stands for CH2, C(CH3)2, C(CF3)2, O, S or SO2,
- R stands for a C1-C5 alkyl group or a halogen group
- n and m are each a number satisfying a requirement represented by the formula 2 ⁇ n + m ⁇ 6 and a and b are each an integer of 1 to 4.
- an ethylene oxide adduct of bisphenol A having a structure represented by the following general formula (3) is preferred. wherein n and m are each a number satisfying a requirement represented by the formula 2 ⁇ n + m ⁇ 6.
- the polyester resin contains, as the diol component units, units of polyoxytetramethylene glycol and/or polyethylene glycol together with ethylene glycol and the ethylene oxide adduct of a bisphenol compound or its derivative.
- the incorporation of polyoxytetramethylene glycol or polyethylene glycol gives rise to the reduction in uneven shrinkage when the polyester resin is used as a heat shrinkable film.
- the content of the polyoxytetramethylene glycol or polyethylene glycol units in the resin is preferably in the range of from 0.1 to 20% by weight, and still preferably in the range of from 0.3 to 15% by weight, because when the polyester resin is used as a heat shrinkable film, if the content of the polyoxytetramethylene glycol or polyethylene glycol is less than 0.1% by weight, the effect of reducing uneven shrinkage is small, while when the content exceeds 20% by weight, the melting point or glass transition point of the resin becomes so low that the film forming properties are lowered.
- the molecular weight of the polyoxytetramethylene glycol used is preferably in the range of from 300 to 4000, and the molecular weight of the polyethylene glycol is preferably in the range of from 300 to 20000, and when the molecular weight is less than the above-described range, no reduction the uneven shrinkage is attained, while when the molecular weight exceeds the above-described range, compatibility with the resin unfavorably becomes poor.
- propylene glycol triethylene glycol, butylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, etc. may also be used as the diol component in such an amount as will not be detrimental to the effect of the present invention.
- the polyester resins according to the first and second inventions preferably contains units of a tricarboxylic or higher polycarboxylic acid, a trihydric or higher polyhydric alcohol or both.
- the content of these polycarboxylic acid and/or polyhydric alcohol units is preferably in the range of from 0.01 to 1% by weight, and still preferably in the range of from 0.05 to 0.7% by weight, because when the polyester resin is used as a heat shrinkable film, if the content of the tricarboxylic or higher polycarboxylic acid and/or trihydric or higher polyhydric alcohol units is less than 0.01% by weight, the effect of reducing uneven shrinkage is small, while if the content exceeds 1% by weight, gelation occurs during polymerization to form a polyester.
- Examples of the polycarboxylic acid used in the present invention include trimellitic acid and pyromellitic acid and their anhydrides.
- Examples of the polyhydric alcohol include trimethylolpropane, glycerin and pentaerythritol. Among them, trimellitic acid, trimethylolpropane and pentaerythritol are particularly preferred from the viewpoint of film forming properties, heat stability, etc.
- the content of the terephthalic acid or its ester forming derivative used as the acid component is preferably 80% by mole or more, and still preferably 90% by mole or more, based on the whole acid component.
- isophthalic acid, naphthalene-1,4- or naphthalene-2,6-dicarboxylic acid, glutaric acid, adipic acid, sebacic acid, oxalic acid, succinic acid and azelaic acid or their ester forming derivatives may be copolymerized as the acid component in an amount that will not be detrimental to the effect of the present invention.
- the ester forming derivative of terephthalic acid or other acids include dialkyl esters and diaryl esters.
- the content of ethylene glycol used as the acid component is in the range of from 2 to 97% by mole, preferably in the range of from 20 to 95% by mole, and still preferably in the range of from 40 to 90% by mole, based on the whole diol component.
- the mechanical properties of the resultant polyester resin are inferior to those of a homopolyester resin, while when the ethylene glycol content exceeds 97% by mole, the effect of improving the crystallinity becomes unsatisfactory, and when the polyester resin is used as a material for direct blow molding, the ethylene glycol content is preferably in the range of from 50 to 90% by mole based on the whole diol component, and when the ethylene glycol content exceeds 90% by mole, the moldability in the direct blow molding is poor and mechanical strength and heat resistance are lowered, while when the ethylene glycol content is less than 50% by mole, the mechanical properties of the homopolyester resin are spoiled.
- the polyester resin of the present invention should contain, as the diol component, an ethylene oxide adduct of bisphenol A represented by the general formula (3).
- the number of moles of added ethylene oxide is preferably in the range of from 2.0 to 2.5.
- the content of the ethylene oxide adduct of bisphenol A copolymerized in the resin is in the range of from 3 to 98% by mole, preferably in the range of from 5 to 80% by mole, and still preferably in the range of from 10 to 60% by mole, based on the whole diol moiety, and when the amount of copolymerization of the ethylene oxide adduct of bisphenol A is less than 3% by mole, no improvement in crystallinity can be attained, while when the amount exceeds 98% by mole, the mechanical properties of the resultant polyester resin become inferior to those of the homopolyester resin and, at the same time, the reactivity is also lowered.
- the content of the ethylene oxide adduct of bisphenol A is preferably in the range of from 10 to 50% by mole based on the whole diol component, and when the content of the ethylene oxide adduct of bisphenol A is less than 10% by mole, the moldability in the direct blow molding becomes poor and, at the same time, mechanical strength and heat resistance are lowered.
- the content of the ethylene oxide of bisphenol A exceeds 50% by mole, the mechanical properties of the homopolyester resin are lowered, which spoils favorable properties in a molded article.
- the content is particularly preferable in the range of from 10 to 40% by mole from the viewpoint of impact resistance.
- the content of the ethylene glycol and ethylene oxide adduct of bisphenol A is preferably 80% by mole or more, and still preferably 90% by mole or more, based on the whole diol component.
- the polyester resin according to the third invention should have an intrinsic viscosity of 0.5 to 1.4 dl/g as measured at 25°C by means of a Ubbelohde viscometer in the form of a solution thereof in a mixed solvent comprising phenol and 1,1,2,2,-tetrachloroethane in a weight ratio of 1 : 1.
- the intrinsic viscosity is preferably in the range of from 0.6 to 1.2 dl/g, and when the intrinsic viscosity is less than 0.5 dl/g, strength thereof after molding becomes low, while when the intrinsic viscosity exceeds 1.4 dl/g, the fluidity becomes so poor that moldability is lowered.
- the diethylene glycol unit content of the polyester resin be 1.2% by weight or less.
- the diethylene glycol unit content is preferably 0.9% by weight or less, and still preferably 0.8% by weight or less.
- polyester resins according to the first to third inventions are produced by a known polymerization method such as transesterification or direct polymerization.
- the resin of the present invention can be produced by charging a reaction vessel with an ester forming derivative of a dicarboxylic acid, such as terephthalic acid, an ethylene oxide adduct of a bisphenol compound or its derivative and ethylene glycol so that the amount of the whole diol component is 1.8 to 2.5 times, by mole, that of the whole acid component, allowing a transesterification reaction to sufficiently proceed at 150 to 250°C in the presence of a transesterification catalyst, adding a stabilizer, a polymerization catalyst, etc. to the reaction system, heating the system to 260 to 300°C under a reduced pressure of 5 mmHg or less and allowing a reaction to proceed for 3 to 5 hr.
- the resin of the present invention can be produced by charging a reaction vessel with terephthalic acid, an ethylene oxide adduct of bisphenol A and ethylene glycol so that the amount of the whole diol component is 1.2 to 1.8 times, by mole, that of the whole acid component, heating the mixture to 150 to 260°C with the system being pressurized by nitrogen to allow the esterification to sufficiently proceed, heating the system to 260 to 300°C under a reduced pressure of 5 mmHg or less and allowing a reaction to proceed for 3 to 5 hr.
- transesterification catalyst used in the production of the polyester resin according to the present invention examples include zinc acetate, manganese acetate, magnesium acetate and titanium tetrabutoxide.
- polymerization catalyst examples include antimony trioxide, titanium tetrabutoxide, dibutyltin oxide and germanium dioxide, and are added in amounts of 50 to 1000 ppm based on the acid component.
- the polyester resin of the present invention can be used as a material for various moldings such as extrusion molding, blow molding, vacuum molding and injection molding and are suitable particularly for use as a heat shrinkable polyester film and a polyester bottle for direct blow molding.
- the treatment include irradiation with ultraviolet rays, ⁇ rays, ⁇ rays, ⁇ rays or an electron beam, treatments such as a corona treatment, a plasma irradiation treatment and a flame treatment, coating of a resin such as vinylidene chloride, polyvinyl alcohol, polyamide or a polyolefin, a laminate and vapor deposition of a metal.
- the additive examples include resins such as polyamides, polyolefins, polymethyl methacrylate and polycarbonate, inorganic particles such as silica, talc, kaolin and calcium carbonate, pigments such as titanium oxide and carbon black, dyes, ultraviolet absorbers, release agents, flame retardants, antioxidants and heat stabilizers.
- polyester resin of the present invention as a heat shrinkable polyester film
- a raw film is formed from the polyester resin of the present invention, preferably the polyester resin according to the first or second invention by a known film forming method, such as a casting roller method or a calender method.
- the raw film is then stretched 1.5 to 5.0 times the original length in the longitudinal direction or the lateral direction, preferably 1.5 to 4.8 times the original length at a temperature of at least 3°C and preferably at least 5°C above the glass transition temperature of the polyester resin to impart a high percentage shrinkage to the film.
- the film is further stretched in a direction normal to the above stretching direction 1.0 to 1.8 times, preferably 1.0 to 1.5 times the original length, which is useful for preventing the film from unnecessarily and excessively shrinking in the above stretching direction through enhancement of the tensile strength of the film.
- the drawing of the film is conducted by simultaneous biaxial stretching, successive biaxial stretching, uniaxial stretching, etc.
- the stretched heat shrinkable polyester film can be used as a product. Alternatively, it may be heat-treated at a temperature of 50 to 150°C for several seconds to several tens of seconds to attain dimensional stability.
- the heat treatment can lead to the development of favorable properties such as the adjustment of percentage shrinkage of the polyester film in the direction of shrinkage, reduction in the shrinkage with the elapse of time during storage of an unshrunk film or reduction in the occurrence of a shrink spot, and although the film thickness is not particularly limited, it is usually in the range of from 1 to 600 ⁇ m from a practical viewpoint.
- packaging applications particularly, in packaging foods, beverages, medicines, etc., use is made of a film having a thickness in the range of from 6 to 380 ⁇ m.
- the percentage shrinkage of the heat shrinkable polyester film of the present invention prepared by the above method is preferably 20% or more at 60°C in a unidirection (in the direction of shrinkage) when the film is heated in a hot bath for 60 sec.
- the percentage shrinkage at 60°C is less than 20%, adhesion to a container is unsatisfactory, so that it becomes necessary to increase the heating temperature during the shrinking step.
- An increase in the heating temperature in the shrinking step gives rise to deformation or a whitening of the container, such as a bottle, and the rapid shrinkage of a heat shrinkable film, which is causative of the occurrence of uneven shrinkage.
- Shrinkage at 60°C is preferably 25% or more, and still preferably 30% or more.
- the shrinking initiation temperature of the heat shrinkable polyester film should be 50°C or below for attaining excellent shrinking properties, because when the heat shrinkable polyester film exhibits a percentage shrinkage of 20% or more at 60°C and a shrinking initiation temperature exceeding 50°C, rapid shrinkage occurs at the time of film shrinkage, which leads to uneven shrinkage.
- the shrinkage at 50°C is preferably at least 1%, and still preferably 2% or more.
- the average shrinking rate be in the range of from 0.3 to 3 %/sec in a period of each 10 sec between 0 sec and 10 sec, between 10 sec and 20 sec and between 20 sec and 30 sec after immersion.
- the heat shrinkable polyester film exhibits shrinkage properties such that, when it is immersed in a hot bath, moderate shrinkage behavior occurs and shrinkage occurs evenly 30 sec after immersion, because when the average shrinkage rate of the film in hot water is less than 0.3 %/sec, and since sufficient shrinkage does not occur, the adhesion of the film to a container is unsatisfactory, so that it is necessary to increase the heating temperature during the shrinking step.
- the average shrinkage rate in hot water is in the range of 0.3 to 3 %/sec in a period of each 10 sec between 0 sec and 10 sec, between 10 sec and 20 sec and between 20 sec and 30 sec after immersion, and the relationship between the immersion time (sec) and the shrinkage (%) is such that the shrinkage increases at a relatively constant rate with the elapse of immersion time and the percentage of increase is relatively moderate. This indicates that when shrinkage for 30 sec after immersion is even, it becomes possible to prevent uneven shrinkage attributable to rapid shrinkage and when moderate shrinkage is maintained for a relatively long period of time, no uneven shrinkage occurs, so that adhesion of the film to a container or the like becomes satisfactory.
- the percentage of shrinkage was determined by providing marked lines at intervals of 100 mm on a polyester film cut out into 150 mm segments in the direction of stretching and 20 mm in a direction normal to the direction of stretching, heating the polyester film in air at 80°C and 100°C (Examples 1 to 9 and Comparative Examples 1 to 8) or hot water at 50 to 90°C (Examples 10 to 19 and Comparative Examples 9 to 15) without a load for 60 sec, measuring the length before shrinkage (L) and the length after shrinkage (L') in the direction of film shrinkage and determining the percentage shrinkage according to the following equation.
- Shrinkage (%) ⁇ (L - L')/L ⁇ ⁇ 100
- a polyester film cut so as to be 150 mm in the direction of stretching and 20 mm in a direction normal to the direction of stretching was heat-shrunk in water at 90°C without application of a load for 60 sec, and the occurrence of uneven shrinkage of the film was evaluated according to the following criteria.
- the solvent-bondability was evaluated by putting both ends of the polyester film on top of the other, bonding the ends to each other by using tetrahydrofuran as an organic solvent, allowing the polyester film to stand for 24 hr, pulling the bonded surface by hand and evaluating the bonding strength according to the following criteria.
- the intrinsic viscosity was measured at 25°C by means of a Ubbelohde viscometer in the form of a solution of the polyester resin dissolved in a mixed solvent comprising phenol and 1,1,2,2-tetrachloroethane in a weight ratio of 1 : 1.
- the glass transition temperature (Tg), melting point (Tm), crystallization peak temperature from a glassy state (Tc+) and crystallization exothermic peak temperature (Tc ⁇ ) from a molten state were determined after raising the temperature of a melt-quenched sample in a nitrogen stream at 280°C at a temperature rise rate of 5°C/min to 280°C in a differential scanning calorimeter (DT-40 manufactured by Shimadzu Seisakusho Ltd.).
- the shoulder value was adopted in the Tg, and the peak value was adopted in the Tm, Tc+ and Tc ⁇ values.
- the impact strength was evaluated in a notch state (impact strength 1) and an unnotched state (impact strength 2) on a specimen of No. 1-A prepared according to a method specified in Izod impact strength (JIS K7110).
- the diethylene glycol content of the resin was measured by decomposing the resin with hydrazine and filtering the decomposition solution and subjecting the filtrate to gas chromatography.
- the moldability was evaluated by setting the resin temperature to 210°C for a non-crystalline resin and 240°C for a crystalline resin, extruding a parison having a length of 200 mm, subjecting the parison to direct blow molding and evaluating 10 molded articles according to the following criteria.
- the oxidation stability was evaluated by subjecting a resin having a water content regulated to 100 ppm or less to extrusion at a resin temperature of 250°C by means of a conventional uniaxial extruder provided with no vent, measuring a change in the IV value between before and after the extrusion and evaluating the oxidation stability in terms of the lowering in the IV value according to the following criteria.
- a reaction vessel was charged with 100 parts by mole of terephthalic acid, 2 parts by mole of an ethylene oxide adduct of bisphenol A, 147 parts by mole of ethylene glycol and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 35 ⁇ m.
- the results of measurement of the percentage shrinkage and the results of evaluation of uneven shrinkage of the resultant film are given in Table 1.
- a reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 30 parts by mole of an ethylene oxide adduct of bisphenol A, 148 parts by mole of ethylene glycol and 20% by weight, based on the polymer, of polyethylene glycol (molecular weight: 10000).
- Zinc acetate was added thereto as a transesterification catalyst in an amount of 350 ppm based on the whole acid component
- germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component
- trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component
- polymerization was conducted by transesterification.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 60°C 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 35 ⁇ m.
- the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are given in Table 1.
- a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 0.3 part by mole of an ethylene oxide adduct of bisphenol A, 141 parts by mole of ethylene glycol and 0.1% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 650), and polymerization and stretching were conducted in the same manner as that of Example 1 to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- a reaction vessel was charged with 83 parts by mole of terephthalic acid, 17 parts by mole of isophthalic acid, 45 parts by mole of an ethylene oxide adduct of bisphenol A, 100 parts by mole of ethylene glycol and 12% by weight, based on the polymer, of polyethylene glycol (molecular weight: 300).
- Germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- a heat shrinkable polyester film having a thickness of 40 ⁇ m was prepared from the resultant polyester resin in the same manner as that of Example 1.
- the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 10 parts by mole of an ethylene oxide adduct of bisphenol S, 150 parts by mole of ethylene glycol and 5% by weight, based on the polymer, of polyethylene glycol (molecular weight: 300).
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid moiety
- germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 70°C 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- a reaction vessel was charged with 100 parts by mole of terephthalic acid, 2 parts by mole of an ethylene oxide adduct of bisphenol A, 147 parts by mole of ethylene glycol, 0.01% by weight, based on the polymer, of trimethylolpropane and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to provide a heat shrinkable polyester film having a thickness of 35 ⁇ m.
- the results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- a reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 30 parts by mole of an ethylene oxide adduct of bisphenol A, 148 parts by mole of ethylene glycol, 0.09% by weight, based on the polymer, of trimellitic anhydride and 20% by weight, based on the polymer, of polyethylene glycol (molecular weight: 10000).
- Zinc acetate was added thereto as a transesterification catalyst in an amount of 350 ppm based on the whole acid component
- germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component
- trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component, and polymerization was conducted by transesterification.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 60°C by 3.8 times the original length in the direction of stretching (direction of TD) to provide a heat shrinkable polyester film having a thickness of 35 ⁇ m.
- the results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 0.2 part by mole of an ethylene oxide adduct of bisphenol A, 141 parts by mole of ethylene glycol, 0.5% by weight, based on the polymer, of pentaerythritol and 0.1% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 650).
- Polymerization and stretching were conducted in the same manner as that of Example 1 to provide a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- a reaction vessel was charged with 83 parts by mole of terephthalic acid, 17 parts by mole of isophthalic acid, 48 parts by mole of an ethylene oxide adduct of bisphenol S, 145 parts by mole of ethylene glycol, 0.7% by weight, based on the polymer, of trimethylolpropane and 12% by weight, based on the polymer, of polyethylene glycol (molecular weight: 300).
- Germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- a heat shrinkable polyester film having a thickness of 40 ⁇ m was prepared from the resultant polyester resin in the same manner as that of Example 1.
- the results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- a reaction vessel was charged with 100 parts by mole of terephthalic acid and 150 parts by mole of ethylene glycol.
- Germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 85°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 2.
- a reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 140 parts by mole of ethylene glycol and 70% by weight, based on the polymer, of polyethylene glycol (molecular weight: 1000), and polymerization was conducted in the same manner as that of Example 2.
- the heat resistance of the resultant polyester resin was so poor that no film could be formed.
- a reaction vessel was charged with 100 parts by mole of terephthalic acid, 100 parts by mole of an ethylene oxide adduct of bisphenol A, 100 parts by mole of ethylene glycol and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component
- trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component
- polymerization was conducted by direct polymerization.
- the degree of polymerization became not increased in the course of the polymerization, so that no polyester resin for forming a film could be obtained.
- a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 20 parts by mole of an ethylene oxide adduct of bisphenol A and 130 parts by mole of ethylene glycol.
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 200 ppm based on the whole acid component
- germanium dioxide was added thereto as a polymerization catalyst in an amount of 400 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 2.
- a reaction vessel was charged with 83 parts by mole of terephthalic acid, 17 parts by mole of isophthalic acid, 130 parts by mole of ethylene glycol and 5% by weight, based on the polymer, of polytetraoxymethylene glycol (molecular weight: 2000).
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 200 ppm based on the whole acid component
- germanium dioxide was added thereto as a polymerization catalyst in an amount of 400 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- a reaction vessel was charged with 100 parts by mole of terephthalic acid, 60 parts by mole of an ethylene oxide adduct of bisphenol A, 140 parts by mole of ethylene glycol, 0.005% by weight, based on the polymer, of trimellitic acid and 0.05% by weight, based on the polymer, of polyethylene glycol (molecular weight: 1000), and polymerization was conducted in the same manner as that of Example 1.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 85°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 2.
- a reaction vessel was charged with 100 parts by mole of terephthalic acid, 50 parts by mole of an ethylene oxide adduct of bisphenol A, 100 parts by mole of ethylene glycol, 10% by weight, based on the polymer, of trimethylolpropane and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component
- trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component
- polymerization was conducted by direct polymerization.
- gelation occurred in the course of the polymerization, so that no polyester resin for forming a film could be prepared.
- a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 42 parts by mole of an ethylene oxide adduct of bisphenol A, 110 parts by mole of ethylene glycol and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 300 ppm based on the whole acid content
- antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid content, and polymerization was conducted by direct polymerization.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 85°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 2.
- a reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of isophthalic acid, 150 parts by mole of ethylene glycol, 2 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Antimony trioxide was added thereto as a polycondensation catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization to give a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 75°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are given in Table 3.
- a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 3 parts by mole of an ethylene oxide adduct of bisphenol A and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 60 ppm based on the whole acid component
- germanium dioxide was added thereto as a polymerization catalyst in an amount of 250 ppm based on the whole acid component.
- Polymerization was conducted by direct polymerization to give a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- a reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component
- antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
- Polymerization was conducted by direct polymerization to give a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
- a reaction vessel was charged with 87 parts by mole of terephthalic acid, 13 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 3 parts by mole of an ethylene oxide adduct of bisphenol A and 5% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component
- antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
- Polymerization was conducted by direct polymerization to give a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
- a reaction vessel was charged with 87 parts by mole of terephthalic acid, 13 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component
- antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
- Polymerization was conducted by direct polymerization to give a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are given in Table 3.
- a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid and 150 parts by mole of ethylene glycol.
- Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
- a heat shrinkable polyester film having a thickness of 40 ⁇ m was prepared from the resultant polyester resin in the same manner as that of Example 1.
- the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
- a reaction vessel was charged with 93 parts by mole of terephthalic acid, 7 parts by mole of isophthalic acid and 140 parts by mole of ethylene glycol. Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 80°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
- a reaction vessel was charged with 100 parts by mole of terephthalic acid, 140 parts by mole of ethylene glycol and 10 parts by mole of an ethylene oxide adduct of bisphenol A. Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 80°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
- a reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of sebacic acid, 140 parts by mole of ethylene glycol and 10 parts by mole of an ethylene oxide adduct of bisphenol A.
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
- Polymerization was conducted by direct polymerization to give a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 80°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
- a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol and 10 parts by mole of an ethylene oxide adduct of bisphenol A. Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to provide a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 80°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film and provided in Table 3.
- a reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of isophthalic acid, 150 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component
- antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
- Polymerization was conducted by direct polymerization to provide a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 4.
- a reaction vessel was charged with 87 parts by mole of terephthalic acid, 13 parts by mole of isophthalic acid, 150 parts by mole of ethylene glycol, 3 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component
- antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
- Polymerization was conducted by direct polymerization to provide a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 4.
- a reaction vessel was charged with 80 parts by mole of terephthalic acid, 15 parts by mole of isophthalic acid, 5 parts by mole of sebacic acid and 150 parts by mole of ethylene glycol.
- Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to provide a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 75°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 4.
- a reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of sebacic acid, 150 parts by mole of ethylene glycol and 20 parts by mole of neopentyl glycol.
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component
- antimony trioxide and zinc acetate were added thereto as a polymerization catalyst in respective amounts of 450 ppm and 100 ppm each based on the whole acid component.
- Polymerization was conducted by direct polymerization to provide a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 75°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 4.
- a reaction vessel was charged with 87 parts by mole of terephthalic acid, 13 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component
- antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
- Polymerization was conducted by direct polymerization to provide a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 60°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and the results of the evaluation of the solvent bondability and uneven shrinkage of the resultant film are provided in Table 5.
- a reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 3 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component
- antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
- Polymerization was conducted by direct polymerization to provide a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 60°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and the results of the evaluation of the solvent bondability and uneven shrinkage of the resultant film are provided in Table 5.
- a reaction vessel was charged with 75 parts by mole of terephthalic acid, 25 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000).
- Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component
- antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
- Polymerization was conducted by direct polymerization to provide a polyester resin.
- the resultant polyester resin was melt-extruded at 270°C to prepare a raw film.
- the raw film was uniaxially stretched at 60°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 ⁇ m.
- the results of the measurement of the percentage shrinkage and the results of the evaluation of the solvent bondability and uneven shrinkage of the resultant film are provided in Table 5.
- a reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 217 parts by mole of ethylene glycol and 3 parts by mole of an ethylene oxide adduct of bisphenol A.
- Zinc acetate was added thereto as a transesterification catalyst in an amount of 300 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C.
- trimethyl phosphate was added thereto as a stabilizer in an amount of 250 ppm based on the whole acid component
- germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
- the system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to give a modified polyester resin.
- the resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- a reaction vessel was charged with 100 parts by mole of terephthalic acid, 145 parts by mole of ethylene glycol and 5 parts by mole of an ethylene oxide adduct of bisphenol A. Esterification was conducted by gradually raising the temperature of the reaction system to 260°C while pressurizing the reaction system with nitrogen. After 94% of the theoretical amount of distilling of water was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 350 ppm based on the whole acid component.
- the system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to give a modified polyester resin.
- the resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- a reaction vessel was charged with 100 parts by mole of terephthalic acid, 120 parts by mole of ethylene glycol and 10 parts by mole of an ethylene oxide adduct of bisphenol A. Esterification was conducted by gradually raising the temperature of the reaction system to 260°C while pressurizing the reaction system with nitrogen. After 92% of the theoretical amount of distilling of water was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 350 ppm based on the whole acid component.
- the system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to provide a modified polyester resin.
- the resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- a reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 190 parts by mole of ethylene glycol and 30 parts by mole of an ethylene oxide adduct of bisphenol A.
- Zinc acetate was added thereto as a transesterification catalyst in an amount of 300 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C.
- trimethyl phosphate was added thereto as a stabilizer in an amount of 250 ppm based on the whole acid component
- antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
- the system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to give a modified polyester resin.
- the resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- a reaction vessel was charged with 100 parts by mole of terephthalic acid, 100 parts by mole of ethylene glycol and 50 parts by mole of an ethylene oxide adduct of bisphenol A. Esterification was conducted by gradually raising the temperature of the reaction system to 260°C while pressurizing the reaction system with nitrogen. After 92% of the theoretical amount of distilling of water was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 350 ppm based on the whole acid component.
- the system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to provide a modified polyester resin.
- the resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- a reaction vessel was charged with 100 parts by mole of methyl naphthalenedicarboxylate, 170 parts by mole of ethylene glycol and 65 parts by mole of an ethylene oxide adduct of bisphenol A.
- Zinc acetate was added thereto as a transesterification catalyst in an amount of 400 ppm based on the whole acid moiety, and transesterification was conducted while gradually raising the temperature of the system to 240°C.
- a reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 130 parts by mole of ethylene glycol and 85 parts by mole of an ethylene oxide adduct of bisphenol A.
- Zinc acetate was added thereto as a transesterification catalyst in an amount of 500 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C.
- trimethyl phosphate was added thereto as a stabilizer in an amount of 400 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 600 ppm based on the whole acid component.
- the system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 4 hr to give a modified polyester resin.
- the resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- a reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 120 parts by mole of ethylene glycol and 100 parts by mole of an ethylene oxide adduct of bisphenol A.
- Zinc acetate was added thereto as a transesterification catalyst in an amount of 500 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C.
- trimethyl phosphate was added thereto as a stabilizer in an amount of 400 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 600 ppm based on the whole acid component.
- the system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 4 hr to provide a modified polyester resin.
- the resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- a reaction vessel was charged with 100 parts by mole of terephthalic acid and 150 parts by mole of ethylene glycol. Esterification was conducted by gradually raising the temperature of the reaction system to 260°C while pressurizing the reaction system with nitrogen. After 92% of the theoretical amount of distilling of water was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 350 ppm based on the whole acid component.
- the system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to provide a modified polyester resin.
- the resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- a reaction vessel was charged with 70 parts by mole of dimethyl terephthalate, 30 parts by mole of dimethyl isophthalate and 220 parts by mole of ethylene glycol.
- Zinc acetate was added thereto as a transesterification catalyst in an amount of 300 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C.
- trimethyl phosphate was added thereto as a stabilizer in an amount of 250 ppm based on the whole acid component
- antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
- the system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to provide a modified polyester resin.
- the resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- a reaction vessel was charged with 70 parts by mole of dimethyl terephthalate, 219 parts by mole of ethylene glycol and 1 part by mole of an ethylene oxide adduct of bisphenol A.
- Zinc acetate was added thereto as a transesterification catalyst in an amount of 300 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C.
- trimethyl phosphate was added thereto as a stabilizer in an amount of 250 ppm based on the whole acid component
- antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component.
- the system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to give a modified polyester resin.
- the resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- a reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 100 parts by mole of ethylene glycol and 120 parts by mole of an ethylene oxide adduct of bisphenol A.
- Zinc acetate was added thereto as a transesterification catalyst in an amount of 600 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C.
- trimethyl phosphate was added thereto as a stabilizer in an amount of 450 ppm based on the whole acid component, and germanium dioxide was added thereto as a polymerization catalyst in an amount of 500 ppm based on the whole acid component.
- the system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to give a modified polyester resin.
- the resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- a reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 185 parts by mole of ethylene glycol and 35 parts by mole of cyclohexanedimethanol.
- Manganese acetate, cobalt acetate and titanium tetrabutoxide were added thereto as a transesterification catalyst in respective amounts of 200 ppm, 330 ppm and 400 ppm each based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C.
- trimethyl phosphate was added thereto as a stabilizer in an amount of 400 ppm based on the whole acid component.
- the system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 4 hr to provide a modified polyester resin.
- the resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- a reaction vessel was charged with 100 parts by mole of terephthalic acid, 250 parts by mole of ethylene glycol and 10 parts by mole of an ethylene oxide adduct of bisphenol A. Esterification was conducted by gradually raising the temperature of the reaction system to 260°C while pressurizing the reaction system with nitrogen. After 92% of the theoretical amount of distilling of water was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 350 ppm based on the whole acid component.
- the system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to give a modified polyester resin.
- the resin composition and properties of the resultant modified polyester resin are provided in Table 6.
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Abstract
Description
- The present invention relates to a polyester resin for use as a molding material for various moldings such as extrusion molding, blow molding, vacuum molding and injection molding, and particularly to a polyester resin suitable for use as a heat shrinkable polyester film for various packaging materials etc. and a bottle for direct blow molding. More particularly, the present invention is concerned with a polyester resin that can be used as a molding material, such as a bottle for direct blow molding, capable of improving crystallinity and, at the same time, moldability and oxidation stability without detriment to mechanical properties of polyethylene terephthalate and can also be used as a highly shrinkable polyester film having high shrinkage in a relatively low temperature region and excellent heat shrinking properties, such as less liability to uneven shrinkage.
- A heat shrinkable plastic film has been used for display, protection, binding, improvement in the added value of goods, etc. in the fields of containers, fishing rods, capacitors, rod-shaped fluorescent lamps, etc. and also for multipack and contact packaging for books, notebooks, etc. At the present time, the development of various applications utilizing the shrinkability and shrinkage stress of the heat shrinkable film is anticipated in many fields other than those described above.
- Resins such as polyvinyl chloride, polystyrene and polyolefin have hitherto been used as a material for a heat shrinkable plastic film. These resins, however, have had problems with heat resistance, weather resistance, chemical resistance, etc. For example, a polyvinyl chloride film is a heat shrinkable film having various shrinking properties. This film, however, is liable to experience the frequent occurrence of fish eye, and goods, wherein the above film subjected to printing is used as a packing material, have a spoiled appearance and a lower value. In order to obtain a heat shrinkable film free from fish eye, it is necessary to conduct excessive quality control, so problems occur such as a significant increase in the production cost of a film. The polyvinyl chloride is disadvantageous also in that incineration at the time of disposal results in a pollution problem, additives such as a plasticizer in polyvinyl chloride bleed out with the elapse of time to cause staining due to deposition of dust etc. and they are unsafe.
- In the heat shrinkable film prepared from polystyrene, although finishing after shrinking is good, the solvent resistance is so low that a special ink should be used for printing. Further, since spontaneous shrinkage occurs even at room temperature, the film should be stored in a cold place. Further, it also had a problem with disposal. Specifically, since incineration at a high temperature is necessary, large amounts of black smoke and an offensive smell are unfavorably generated at the time of the incineration.
- A polyester film is greatly expected as a material capable of solving the above-described problems, and the amount of use thereof has increased. In the conventional heat shrinkable polyester film, use was made of a copolymer polyester resin comprising a dicarboxylic acid moiety composed mainly of terephthalic acid and a diol moiety composed mainly of ethylene glycol and, copolymerized with the dicarboxylic acid moiety, isophthalic acid, sebacic acid, adipic acid or neopentyl glycol. The conventional heat shrinkable polyester film, however, had no satisfactory heat shrinking properties. In particular, uneven shrinkage is liable to occur during shrinkage. For this reason, when the film covers a container, such as a bottle, and then shrunk, there occurs a problem in that letters or patterns printed on the film are distorted and the adhesion of the film to the container is unsatisfactory.
- Further, compared with the polystyrene film, the polyester film is inferior regarding shrinkability at a low temperature and therefore should be shrunk at a high temperature in order to attain the necessary degree of shrinkage, which gives rise to such problems as deformation and bottle whitening etc. In particular, when the polyester film is used as a label for a polyethylene bottle, since the polyethylene bottle, as such, is inferior to a PET bottle etc. in heat resistance, the shrinking operation should be conducted at the relatively low temperature of about 70°C. For this reason, the development of a heat shrinkable film having excellent shrinking properties at a low temperature has been desired in the art.
- As described in Japanese Unexamined Patent Publication (Kokai) Nos. 63-168329 and 1-136721, a heat shrinkable film comprising a copolymer polyester has been developed wherein an ethylene oxide adduct of a bisphenol compound or an ethylene oxide adduct of a bisphenol derivative is used as a comonomer component and the retention time of residual stress at the time of the heat treatment is prolonged so as to improve the shrinking properties. Even in the heat shrinkable polyester film comprising the above-described copolymer polymer, alleviation in uneven shrinkage is unsatisfactory, and a high percent of shrinkage cannot be attained at a low temperature of about 70°C.
- Polyethylene terephthalate, polybutylene terephthalate, etc. have generally been used as a polyester resin for a molding material used in direct blow molding or the like. Further, modified polyester resins comprising said resins copolymerized with various monomers, such as isophthalic acid or cyclohexanedimethanol, polyethylene naphthalate comprising an acid moiety composed mainly of naphthalenedicarboxylic acid, etc. have been developed.
- In the modified polyester resins copolymerized with isophthalic acid, however, the mechanical strength properties, such as impact strength, deteriorate with an increase in the amount of isophthalic acid. Further, when direct blow molding is conducted, and since the melt viscosity of the resin is so low that it is very difficult to conduct molding, a comparison cannot be formed, and in particular, a large container cannot be molded. The modified polyester resin copolymerized with cyclohexanedimethanol is unsatisfactory although an improvement in moldability can be attained over that of a resin copolymerized with isophthalic acid. Further, the heat stability of the resin is so poor that when the resin stays within a molding machine for a long period of time, the deterioration of the resin is significant. Polyethylene naphthalate has the feature that it has a higher melting point than the conventional polyester resins, but, it is unsatisfactory as a resin for a molding material with respect to mechanical properties and moldability.
- Further, in the polyester resin wherein ethylene glycol is used as a diol moiety, diethylene glycol produced as a by-product is contained in the resin, which leads to a lowering in the moldability and oxidation stability of the resin. An attempt to reduce the diethylene glycol content has been made by the addition of sodium hydroxide or the like during polymerization. Even a polyester resin produced by this method is unsatisfactory with respect to the moldability or oxidation stability although it is possible to reduce the diethylene glycol content to about 1.5% by weight.
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- The present invention provides first a polyester resin comprising units of a dicarboxylic acid component composed mainly of an aromatic dicarboxylic acid or its ester forming derivative and a diol component composed mainly of ethylene glycol and an ethylene oxide adduct of a bisphenol compound or its derivative; the content of the ethylene oxide adduct of a bisphenol compound or its derivative being 0.1 to 50% by mole based on the whole diol component, and said resin further comprising 0.1 to 20% by weight of units of polyoxytetramethylene glycol and/or polyethylene glycol.
- The invention also provides a polyester resin comprising units of a dicarboxylic and component composed mainly of an aromatic dicarboxylic acid or its ester forming derivative and a diol component composed mainly of ethylene glycol and an ethylene oxide adduct of a bisphenol compound or its derivative; the content of the ethylene oxide adduct of a bisphenol compound or its derivative being 0.1 to 50% by mole based on the whole diol component, and said resin further comprising units of a tricarboxylic or higher polycarboxylic acid and/or a trihydric or higher polyhydric alcohol.
- The invention also provides a polyester resin comprising units of an acid component composed mainly of terephthalic acid or its ester forming derivative and a diol component composed mainly of ethylene glycol and an ethylene oxide adduct of bisphenol A; the content of the ethylene oxide adduct of bisphenol A being 3 to 98% by mole based on the whole diol component, and said polyester resin having an intrinsic viscosity of 0.5 to 1.4 dl/g and a diethylene glycol unit content of 1.2% by weight or less.
- The polyester resin of the present invention comprises units of a dicarboxylic acid component composed mainly of an aromatic dicarboxylic acid or its ester forming derivative and a diol component composed mainly of ethylene glycol and an ethylene oxide adduct of a bisphenol compound or its derivative.
- At the outset, the polyester resins according to the first and second inventions will now be described. Examples of the aromatic dicarboxylic acid as a main component of the dicarboxylic acid component constituting the polyester resins according to the first and second inventions include terephthalic acid, isophthalic acid and naphthalene-1,4- and naphthalene-2,6-dicarboxylic acids. Examples of the ester forming derivatives thereof include derivatives such as dialkyl esters and diaryl esters. The content of these aromatic dicarboxylic acids or their ester forming derivatives in the dicarboxylic acid component is preferably 80% by mole or more, still preferably 85% by mole or more, and when the content of the aromatic dicarboxylic acid or its ester forming derivative is less than 80% by mole, there is a tendency, when it is formed into, for example, a film, to lower the mechanical strength of the polyester film.
- The dicarboxylic acid component preferably includes terephthalic acid and isophthalic acid or their ester forming derivative. In this case, the content of the isophthalic acid or its ester forming derivative based on the whole dicarboxylic acid component is in the range of from 7 to 30% by mole, preferably in the range of from 10 to 30% by mole, still preferably in the range of from 12 to 30% by mole, because when the polyester resin is used as a heat shrinkable label for a container such as a bottle, the heat shrinkable film is used after the ends of the film are solvent-bonded to each other with a solvent, such as tetrahydrofuran, so as render the film in tubular form. Therefore, when the ends are not sufficiently bonded to each other, the label is unfavorably peeled off. The content of isophthalic acid or its ester forming derivative was limited to the above-described range for the purpose of imparting a sufficient solvent-bonding property to the film, and when the content is less than 7% by mole, no sufficient improvement in the solvent-bonding property can be attained. On the other hand, when the content exceeds 30% by mole, shrinking properties, such as uneven and high percentage shrinkage become poor.
- In the polyester resin of the present invention, aliphatic dicarboxylic acids or their ester forming derivatives other than those described above may be incorporated in an amount of less than 20% by mole, preferably less than 15% by mole for the purpose of enhancing the effect of the present invention. When these aliphatic dicarboxylic acids are incorporated in an amount of 20% by mole or more, there is a possibility that when the polyester resin is formed into a film, the mechanical properties of the film are lowered. Examples of the aliphatic dicarboxylic acid useable in the present invention include glutaric acid, adipic acid, sebacic acid, azelaic acid, oxalic acid and succinic acid, and when the polyester resin is used as a heat shrinkable film, the incorporation of these aliphatic dicarboxylic acids or their ester forming derivatives in a suitable amount contributes to the enhancement of the percentage heat shrinkage.
- The diol component constituting the polyester resin according to the first and second inventions should be composed mainly of ethylene glycol and an ethylene oxide adduct of a bisphenol compound or its derivative, and the content of the ethylene oxide adduct of the bisphenol compound or its derivative should be in the range of from 0.1 to 50% by mole, preferably in the range of from 0.5 to 30% by mole based on the whole diol component, because when the polyester resin is used as a heat shrinkable film, if the content of the ethylene oxide adduct of bisphenol A is less than 0.1% by mole, no effect of reducing the uneven shrinkage can be attained, while if the content exceeds 50% by mole, shrinkage at a low temperature is lowered. Examples of the ethylene oxide adduct of the bisphenol compound or its derivative include those having structures represented by the following general formulae (1) and (2).
wherein X stands for CH₂, C(CH₃)₂, C(CF₃)₂, O, S or SO₂ and n and m are each a number satisfying a requirement represented by the formula 2 ≦ n + m ≦ 6.
wherein X stands for CH₂, C(CH₃)₂, C(CF₃)₂, O, S or SO₂, R stands for a C₁-C₅ alkyl group or a halogen group, n and m are each a number satisfying a requirement represented by the formula 2 ≦ n + m ≦ 6 and a and b are each an integer of 1 to 4. -
- In the present invention, the polyester resin contains, as the diol component units, units of polyoxytetramethylene glycol and/or polyethylene glycol together with ethylene glycol and the ethylene oxide adduct of a bisphenol compound or its derivative. The incorporation of polyoxytetramethylene glycol or polyethylene glycol gives rise to the reduction in uneven shrinkage when the polyester resin is used as a heat shrinkable film. The content of the polyoxytetramethylene glycol or polyethylene glycol units in the resin is preferably in the range of from 0.1 to 20% by weight, and still preferably in the range of from 0.3 to 15% by weight, because when the polyester resin is used as a heat shrinkable film, if the content of the polyoxytetramethylene glycol or polyethylene glycol is less than 0.1% by weight, the effect of reducing uneven shrinkage is small, while when the content exceeds 20% by weight, the melting point or glass transition point of the resin becomes so low that the film forming properties are lowered. The molecular weight of the polyoxytetramethylene glycol used is preferably in the range of from 300 to 4000, and the molecular weight of the polyethylene glycol is preferably in the range of from 300 to 20000, and when the molecular weight is less than the above-described range, no reduction the uneven shrinkage is attained, while when the molecular weight exceeds the above-described range, compatibility with the resin unfavorably becomes poor.
- Further, according to the present invention, propylene glycol, triethylene glycol, butylene glycol, diethylene glycol, neopentyl glycol, cyclohexanedimethanol, etc. may also be used as the diol component in such an amount as will not be detrimental to the effect of the present invention.
- The polyester resins according to the first and second inventions preferably contains units of a tricarboxylic or higher polycarboxylic acid, a trihydric or higher polyhydric alcohol or both. The content of these polycarboxylic acid and/or polyhydric alcohol units is preferably in the range of from 0.01 to 1% by weight, and still preferably in the range of from 0.05 to 0.7% by weight, because when the polyester resin is used as a heat shrinkable film, if the content of the tricarboxylic or higher polycarboxylic acid and/or trihydric or higher polyhydric alcohol units is less than 0.01% by weight, the effect of reducing uneven shrinkage is small, while if the content exceeds 1% by weight, gelation occurs during polymerization to form a polyester.
- Examples of the polycarboxylic acid used in the present invention include trimellitic acid and pyromellitic acid and their anhydrides. Examples of the polyhydric alcohol include trimethylolpropane, glycerin and pentaerythritol. Among them, trimellitic acid, trimethylolpropane and pentaerythritol are particularly preferred from the viewpoint of film forming properties, heat stability, etc.
- The polyester resin according to the third invention will now be described. In the polyester resin according to the third invention, the content of the terephthalic acid or its ester forming derivative used as the acid component is preferably 80% by mole or more, and still preferably 90% by mole or more, based on the whole acid component. In the present invention, for example, isophthalic acid, naphthalene-1,4- or naphthalene-2,6-dicarboxylic acid, glutaric acid, adipic acid, sebacic acid, oxalic acid, succinic acid and azelaic acid or their ester forming derivatives may be copolymerized as the acid component in an amount that will not be detrimental to the effect of the present invention. Examples of the ester forming derivative of terephthalic acid or other acids include dialkyl esters and diaryl esters.
- The content of ethylene glycol used as the acid component is in the range of from 2 to 97% by mole, preferably in the range of from 20 to 95% by mole, and still preferably in the range of from 40 to 90% by mole, based on the whole diol component. When the ethylene glycol content is less than 2% by mole, the mechanical properties of the resultant polyester resin are inferior to those of a homopolyester resin, while when the ethylene glycol content exceeds 97% by mole, the effect of improving the crystallinity becomes unsatisfactory, and when the polyester resin is used as a material for direct blow molding, the ethylene glycol content is preferably in the range of from 50 to 90% by mole based on the whole diol component, and when the ethylene glycol content exceeds 90% by mole, the moldability in the direct blow molding is poor and mechanical strength and heat resistance are lowered, while when the ethylene glycol content is less than 50% by mole, the mechanical properties of the homopolyester resin are spoiled.
- The polyester resin of the present invention should contain, as the diol component, an ethylene oxide adduct of bisphenol A represented by the general formula (3). The number of moles of added ethylene oxide is preferably in the range of from 2.0 to 2.5. The content of the ethylene oxide adduct of bisphenol A copolymerized in the resin is in the range of from 3 to 98% by mole, preferably in the range of from 5 to 80% by mole, and still preferably in the range of from 10 to 60% by mole, based on the whole diol moiety, and when the amount of copolymerization of the ethylene oxide adduct of bisphenol A is less than 3% by mole, no improvement in crystallinity can be attained, while when the amount exceeds 98% by mole, the mechanical properties of the resultant polyester resin become inferior to those of the homopolyester resin and, at the same time, the reactivity is also lowered. When the polyester resin is used as direct blow molding, the content of the ethylene oxide adduct of bisphenol A is preferably in the range of from 10 to 50% by mole based on the whole diol component, and when the content of the ethylene oxide adduct of bisphenol A is less than 10% by mole, the moldability in the direct blow molding becomes poor and, at the same time, mechanical strength and heat resistance are lowered. On the other hand, when the content of the ethylene oxide of bisphenol A exceeds 50% by mole, the mechanical properties of the homopolyester resin are lowered, which spoils favorable properties in a molded article. The content is particularly preferable in the range of from 10 to 40% by mole from the viewpoint of impact resistance.
- Further, it is also possible to copolymerize neopentyl glycol, propylene glycol, polyoxytetramethylene glycol, polyethylene glycol, cyclohexanedimethanol, etc. in an amount that will not be detrimental to the effect of the present invention. However, the content of the ethylene glycol and ethylene oxide adduct of bisphenol A is preferably 80% by mole or more, and still preferably 90% by mole or more, based on the whole diol component.
- The polyester resin according to the third invention should have an intrinsic viscosity of 0.5 to 1.4 dl/g as measured at 25°C by means of a Ubbelohde viscometer in the form of a solution thereof in a mixed solvent comprising phenol and 1,1,2,2,-tetrachloroethane in a weight ratio of 1 : 1. The intrinsic viscosity is preferably in the range of from 0.6 to 1.2 dl/g, and when the intrinsic viscosity is less than 0.5 dl/g, strength thereof after molding becomes low, while when the intrinsic viscosity exceeds 1.4 dl/g, the fluidity becomes so poor that moldability is lowered.
- It is important that the diethylene glycol unit content of the polyester resin be 1.2% by weight or less. When the diethylene glycol unit content exceeds 1.2% by weight, the moldability of the resin is lowered and also the oxidation stability, mechanical strength and heat resistance are lowered. The diethylene glycol unit content is preferably 0.9% by weight or less, and still preferably 0.8% by weight or less.
- The above-described polyester resins according to the first to third inventions are produced by a known polymerization method such as transesterification or direct polymerization. In the transesterification method, the resin of the present invention can be produced by charging a reaction vessel with an ester forming derivative of a dicarboxylic acid, such as terephthalic acid, an ethylene oxide adduct of a bisphenol compound or its derivative and ethylene glycol so that the amount of the whole diol component is 1.8 to 2.5 times, by mole, that of the whole acid component, allowing a transesterification reaction to sufficiently proceed at 150 to 250°C in the presence of a transesterification catalyst, adding a stabilizer, a polymerization catalyst, etc. to the reaction system, heating the system to 260 to 300°C under a reduced pressure of 5 mmHg or less and allowing a reaction to proceed for 3 to 5 hr.
- In the direct polymerization method, the resin of the present invention can be produced by charging a reaction vessel with terephthalic acid, an ethylene oxide adduct of bisphenol A and ethylene glycol so that the amount of the whole diol component is 1.2 to 1.8 times, by mole, that of the whole acid component, heating the mixture to 150 to 260°C with the system being pressurized by nitrogen to allow the esterification to sufficiently proceed, heating the system to 260 to 300°C under a reduced pressure of 5 mmHg or less and allowing a reaction to proceed for 3 to 5 hr.
- Examples of the transesterification catalyst used in the production of the polyester resin according to the present invention include zinc acetate, manganese acetate, magnesium acetate and titanium tetrabutoxide. Examples of the polymerization catalyst include antimony trioxide, titanium tetrabutoxide, dibutyltin oxide and germanium dioxide, and are added in amounts of 50 to 1000 ppm based on the acid component.
- The polyester resin of the present invention can be used as a material for various moldings such as extrusion molding, blow molding, vacuum molding and injection molding and are suitable particularly for use as a heat shrinkable polyester film and a polyester bottle for direct blow molding. In order to impart a particular performance to these moldings, it is also possible to conduct various known treatments or incorporate suitable additives. Examples of the treatment include irradiation with ultraviolet rays, α rays, β rays, γ rays or an electron beam, treatments such as a corona treatment, a plasma irradiation treatment and a flame treatment, coating of a resin such as vinylidene chloride, polyvinyl alcohol, polyamide or a polyolefin, a laminate and vapor deposition of a metal. Examples of the additive include resins such as polyamides, polyolefins, polymethyl methacrylate and polycarbonate, inorganic particles such as silica, talc, kaolin and calcium carbonate, pigments such as titanium oxide and carbon black, dyes, ultraviolet absorbers, release agents, flame retardants, antioxidants and heat stabilizers.
- Use of the polyester resin of the present invention as a heat shrinkable polyester film will now be described.
- In the case of the heat shrinkable polyester film, a raw film is formed from the polyester resin of the present invention, preferably the polyester resin according to the first or second invention by a known film forming method, such as a casting roller method or a calender method. The raw film is then stretched 1.5 to 5.0 times the original length in the longitudinal direction or the lateral direction, preferably 1.5 to 4.8 times the original length at a temperature of at least 3°C and preferably at least 5°C above the glass transition temperature of the polyester resin to impart a high percentage shrinkage to the film. If necessary, the film is further stretched in a direction normal to the above stretching direction 1.0 to 1.8 times, preferably 1.0 to 1.5 times the original length, which is useful for preventing the film from unnecessarily and excessively shrinking in the above stretching direction through enhancement of the tensile strength of the film. The drawing of the film is conducted by simultaneous biaxial stretching, successive biaxial stretching, uniaxial stretching, etc.
- The stretched heat shrinkable polyester film, as such, can be used as a product. Alternatively, it may be heat-treated at a temperature of 50 to 150°C for several seconds to several tens of seconds to attain dimensional stability. The heat treatment can lead to the development of favorable properties such as the adjustment of percentage shrinkage of the polyester film in the direction of shrinkage, reduction in the shrinkage with the elapse of time during storage of an unshrunk film or reduction in the occurrence of a shrink spot, and although the film thickness is not particularly limited, it is usually in the range of from 1 to 600 µm from a practical viewpoint. In packaging applications, particularly, in packaging foods, beverages, medicines, etc., use is made of a film having a thickness in the range of from 6 to 380 µm. In the case of use as a label for PET bottles, glass bottles, etc., use is made of a film having a thickness in the range of from 20 to 70 µm.
- The percentage shrinkage of the heat shrinkable polyester film of the present invention prepared by the above method is preferably 20% or more at 60°C in a unidirection (in the direction of shrinkage) when the film is heated in a hot bath for 60 sec. When the percentage shrinkage at 60°C is less than 20%, adhesion to a container is unsatisfactory, so that it becomes necessary to increase the heating temperature during the shrinking step. An increase in the heating temperature in the shrinking step gives rise to deformation or a whitening of the container, such as a bottle, and the rapid shrinkage of a heat shrinkable film, which is causative of the occurrence of uneven shrinkage. Shrinkage at 60°C is preferably 25% or more, and still preferably 30% or more.
- The shrinking initiation temperature of the heat shrinkable polyester film should be 50°C or below for attaining excellent shrinking properties, because when the heat shrinkable polyester film exhibits a percentage shrinkage of 20% or more at 60°C and a shrinking initiation temperature exceeding 50°C, rapid shrinkage occurs at the time of film shrinkage, which leads to uneven shrinkage. The shrinkage at 50°C is preferably at least 1%, and still preferably 2% or more.
- Further, it is preferred that when the heat shrinkable polyester film is immersed, for example, in a hot bath of 60°C, the average shrinking rate be in the range of from 0.3 to 3 %/sec in a period of each 10 sec between 0 sec and 10 sec, between 10 sec and 20 sec and between 20 sec and 30 sec after immersion. Specifically, the heat shrinkable polyester film exhibits shrinkage properties such that, when it is immersed in a hot bath, moderate shrinkage behavior occurs and shrinkage occurs evenly 30 sec after immersion, because when the average shrinkage rate of the film in hot water is less than 0.3 %/sec, and since sufficient shrinkage does not occur, the adhesion of the film to a container is unsatisfactory, so that it is necessary to increase the heating temperature during the shrinking step. An increase in the heating temperature during the shrinking step gives rise to deformation or whitening of a container such as a bottle and, at the same time, gives rise to rapid shrinkage of a heat shrinkable film, which is causative of the occurrence of uneven shrinkage. On the other hand, when the average shrinkage rate of the film in hot water exceeds 3 %/sec, the shrinkage of the film becomes rapid, so that uneven shrinkage occurs.
- In the heat shrinkable polyester film of the present invention, the average shrinkage rate in hot water is in the range of 0.3 to 3 %/sec in a period of each 10 sec between 0 sec and 10 sec, between 10 sec and 20 sec and between 20 sec and 30 sec after immersion, and the relationship between the immersion time (sec) and the shrinkage (%) is such that the shrinkage increases at a relatively constant rate with the elapse of immersion time and the percentage of increase is relatively moderate. This indicates that when shrinkage for 30 sec after immersion is even, it becomes possible to prevent uneven shrinkage attributable to rapid shrinkage and when moderate shrinkage is maintained for a relatively long period of time, no uneven shrinkage occurs, so that adhesion of the film to a container or the like becomes satisfactory.
- The present invention will be further illustrated with reference to the following non-limitative Examples.
- In the Examples, the percentage of shrinkage was determined by providing marked lines at intervals of 100 mm on a polyester film cut out into 150 mm segments in the direction of stretching and 20 mm in a direction normal to the direction of stretching, heating the polyester film in air at 80°C and 100°C (Examples 1 to 9 and Comparative Examples 1 to 8) or hot water at 50 to 90°C (Examples 10 to 19 and Comparative Examples 9 to 15) without a load for 60 sec, measuring the length before shrinkage (L) and the length after shrinkage (L') in the direction of film shrinkage and determining the percentage shrinkage according to the following equation.
With respect to uneven shrinkage, a polyester film cut so as to be 150 mm in the direction of stretching and 20 mm in a direction normal to the direction of stretching was heat-shrunk in water at 90°C without application of a load for 60 sec, and the occurrence of uneven shrinkage of the film was evaluated according to the following criteria. - ⓞ:
- No uneven shrinkage was observed.
- ⃝:
- Substantially no uneven shrinkage was observed.
- △:
- Some uneven shrinkage was observed.
- ×:
- Remarkable uneven shrinkage was observed.
- The solvent-bondability was evaluated by putting both ends of the polyester film on top of the other, bonding the ends to each other by using tetrahydrofuran as an organic solvent, allowing the polyester film to stand for 24 hr, pulling the bonded surface by hand and evaluating the bonding strength according to the following criteria.
- ⓞ:
- Bonding strength was excellent.
- ⃝:
- Sufficient bonding strength was obtained.
- △:
- Bonding strength was relatively small.
- ×:
- Bonding strength was unsatisfactory or no bonding was attained.
- The intrinsic viscosity was measured at 25°C by means of a Ubbelohde viscometer in the form of a solution of the polyester resin dissolved in a mixed solvent comprising phenol and 1,1,2,2-tetrachloroethane in a weight ratio of 1 : 1.
- The glass transition temperature (Tg), melting point (Tm), crystallization peak temperature from a glassy state (Tc⁺) and crystallization exothermic peak temperature (Tc⁻) from a molten state were determined after raising the temperature of a melt-quenched sample in a nitrogen stream at 280°C at a temperature rise rate of 5°C/min to 280°C in a differential scanning calorimeter (DT-40 manufactured by Shimadzu Seisakusho Ltd.). The shoulder value was adopted in the Tg, and the peak value was adopted in the Tm, Tc⁺ and Tc⁻ values.
- The impact strength was evaluated in a notch state (impact strength 1) and an unnotched state (impact strength 2) on a specimen of No. 1-A prepared according to a method specified in Izod impact strength (JIS K7110).
- The diethylene glycol content of the resin was measured by decomposing the resin with hydrazine and filtering the decomposition solution and subjecting the filtrate to gas chromatography.
- The moldability was evaluated by setting the resin temperature to 210°C for a non-crystalline resin and 240°C for a crystalline resin, extruding a parison having a length of 200 mm, subjecting the parison to direct blow molding and evaluating 10 molded articles according to the following criteria.
- ⓞ:
- All the 10 molded articles were acceptable.
- ⃝:
- 9 out of the 10 molded articles were acceptable.
- △:
- 7 out of the 10 molded articles were acceptable.
- ×:
- 6 out of the 10 molded articles were acceptable.
- The oxidation stability was evaluated by subjecting a resin having a water content regulated to 100 ppm or less to extrusion at a resin temperature of 250°C by means of a conventional uniaxial extruder provided with no vent, measuring a change in the IV value between before and after the extrusion and evaluating the oxidation stability in terms of the lowering in the IV value according to the following criteria.
- A:
- The lowering in the IV value was less than 5%.
- B:
- The lowering in the IV value was 5% to 10% exclusive.
- C:
- The lowering in the IV value was 10% or more.
- In the following Examples, an ethylene oxide adduct of bisphenol A represented by the general formula (3) or an ethylene oxide adduct of bisphenol S represented by the general formula (1) wherein n + m = 2 was used as the ethylene oxide adduct of the bisphenol compound or its derivative.
- A reaction vessel was charged with 100 parts by mole of terephthalic acid, 2 parts by mole of an ethylene oxide adduct of bisphenol A, 147 parts by mole of ethylene glycol and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 35 µm. The results of measurement of the percentage shrinkage and the results of evaluation of uneven shrinkage of the resultant film are given in Table 1.
- A reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 30 parts by mole of an ethylene oxide adduct of bisphenol A, 148 parts by mole of ethylene glycol and 20% by weight, based on the polymer, of polyethylene glycol (molecular weight: 10000). Zinc acetate was added thereto as a transesterification catalyst in an amount of 350 ppm based on the whole acid component, germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component, and polymerization was conducted by transesterification.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 60°C 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 35 µm. The results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are given in Table 1.
- A reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 0.3 part by mole of an ethylene oxide adduct of bisphenol A, 141 parts by mole of ethylene glycol and 0.1% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 650), and polymerization and stretching were conducted in the same manner as that of Example 1 to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- A reaction vessel was charged with 83 parts by mole of terephthalic acid, 17 parts by mole of isophthalic acid, 45 parts by mole of an ethylene oxide adduct of bisphenol A, 100 parts by mole of ethylene glycol and 12% by weight, based on the polymer, of polyethylene glycol (molecular weight: 300). Germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- A heat shrinkable polyester film having a thickness of 40 µm was prepared from the resultant polyester resin in the same manner as that of Example 1. The results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- A reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 10 parts by mole of an ethylene oxide adduct of bisphenol S, 150 parts by mole of ethylene glycol and 5% by weight, based on the polymer, of polyethylene glycol (molecular weight: 300). Trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid moiety, germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 70°C 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- A reaction vessel was charged with 100 parts by mole of terephthalic acid, 2 parts by mole of an ethylene oxide adduct of bisphenol A, 147 parts by mole of ethylene glycol, 0.01% by weight, based on the polymer, of trimethylolpropane and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to provide a heat shrinkable polyester film having a thickness of 35 µm. The results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- A reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 30 parts by mole of an ethylene oxide adduct of bisphenol A, 148 parts by mole of ethylene glycol, 0.09% by weight, based on the polymer, of trimellitic anhydride and 20% by weight, based on the polymer, of polyethylene glycol (molecular weight: 10000). Zinc acetate was added thereto as a transesterification catalyst in an amount of 350 ppm based on the whole acid component, germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component, and polymerization was conducted by transesterification.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 60°C by 3.8 times the original length in the direction of stretching (direction of TD) to provide a heat shrinkable polyester film having a thickness of 35 µm. The results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- A reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 0.2 part by mole of an ethylene oxide adduct of bisphenol A, 141 parts by mole of ethylene glycol, 0.5% by weight, based on the polymer, of pentaerythritol and 0.1% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 650). Polymerization and stretching were conducted in the same manner as that of Example 1 to provide a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- A reaction vessel was charged with 83 parts by mole of terephthalic acid, 17 parts by mole of isophthalic acid, 48 parts by mole of an ethylene oxide adduct of bisphenol S, 145 parts by mole of ethylene glycol, 0.7% by weight, based on the polymer, of trimethylolpropane and 12% by weight, based on the polymer, of polyethylene glycol (molecular weight: 300). Germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- A heat shrinkable polyester film having a thickness of 40 µm was prepared from the resultant polyester resin in the same manner as that of Example 1. The results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- A reaction vessel was charged with 100 parts by mole of terephthalic acid and 150 parts by mole of ethylene glycol. Germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 85°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 2.
- A reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 140 parts by mole of ethylene glycol and 70% by weight, based on the polymer, of polyethylene glycol (molecular weight: 1000), and polymerization was conducted in the same manner as that of Example 2. The heat resistance of the resultant polyester resin was so poor that no film could be formed.
- A reaction vessel was charged with 100 parts by mole of terephthalic acid, 100 parts by mole of an ethylene oxide adduct of bisphenol A, 100 parts by mole of ethylene glycol and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component, and polymerization was conducted by direct polymerization. However, the degree of polymerization became not increased in the course of the polymerization, so that no polyester resin for forming a film could be obtained.
- A reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 20 parts by mole of an ethylene oxide adduct of bisphenol A and 130 parts by mole of ethylene glycol. Trimethyl phosphate was added thereto as a stabilizer in an amount of 200 ppm based on the whole acid component, germanium dioxide was added thereto as a polymerization catalyst in an amount of 400 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 2.
- A reaction vessel was charged with 83 parts by mole of terephthalic acid, 17 parts by mole of isophthalic acid, 130 parts by mole of ethylene glycol and 5% by weight, based on the polymer, of polytetraoxymethylene glycol (molecular weight: 2000). Trimethyl phosphate was added thereto as a stabilizer in an amount of 200 ppm based on the whole acid component, germanium dioxide was added thereto as a polymerization catalyst in an amount of 400 ppm based on the whole acid component, and polymerization was conducted by direct polymerization.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- A reaction vessel was charged with 100 parts by mole of terephthalic acid, 60 parts by mole of an ethylene oxide adduct of bisphenol A, 140 parts by mole of ethylene glycol, 0.005% by weight, based on the polymer, of trimellitic acid and 0.05% by weight, based on the polymer, of polyethylene glycol (molecular weight: 1000), and polymerization was conducted in the same manner as that of Example 1.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 85°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 2.
- A reaction vessel was charged with 100 parts by mole of terephthalic acid, 50 parts by mole of an ethylene oxide adduct of bisphenol A, 100 parts by mole of ethylene glycol, 10% by weight, based on the polymer, of trimethylolpropane and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component, trimethyl phosphate was added thereto as a stabilizer in an amount of 350 ppm based on the whole acid component, and polymerization was conducted by direct polymerization. However, gelation occurred in the course of the polymerization, so that no polyester resin for forming a film could be prepared.
- A reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 42 parts by mole of an ethylene oxide adduct of bisphenol A, 110 parts by mole of ethylene glycol and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Trimethyl phosphate was added thereto as a stabilizer in an amount of 300 ppm based on the whole acid content, antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid content, and polymerization was conducted by direct polymerization.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 85°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage maximum shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 2.
- The components listed in the tables are as follows.
- TPA:
- terephthalic acid
- IPA:
- isophthalic acid
- EG :
- ethylene glycol
- BPAE:
- ethylene oxide adduct of bisphenol A
- BPSE:
- ethylene oxide adduct of bisphenol S
- PEG:
- polyethylene glycol
- PTMG:
- polyoxytetramethylene glycol
- TMA:
- trimellitic acid
- TMP:
- trimethylolpropane
- PEN:
- pentaerythritol
- A reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of isophthalic acid, 150 parts by mole of ethylene glycol, 2 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Antimony trioxide was added thereto as a polycondensation catalyst in an amount of 450 ppm based on the whole acid component, and polymerization was conducted by direct polymerization to give a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 75°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are given in Table 3.
- A reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 3 parts by mole of an ethylene oxide adduct of bisphenol A and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Trimethyl phosphate was added thereto as a stabilizer in an amount of 60 ppm based on the whole acid component, and germanium dioxide was added thereto as a polymerization catalyst in an amount of 250 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 1.
- A reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
- A reaction vessel was charged with 87 parts by mole of terephthalic acid, 13 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 3 parts by mole of an ethylene oxide adduct of bisphenol A and 5% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
- A reaction vessel was charged with 87 parts by mole of terephthalic acid, 13 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are given in Table 3.
- A reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid and 150 parts by mole of ethylene glycol. Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
- A heat shrinkable polyester film having a thickness of 40 µm was prepared from the resultant polyester resin in the same manner as that of Example 1. The results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
- A reaction vessel was charged with 93 parts by mole of terephthalic acid, 7 parts by mole of isophthalic acid and 140 parts by mole of ethylene glycol. Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 80°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
- A reaction vessel was charged with 100 parts by mole of terephthalic acid, 140 parts by mole of ethylene glycol and 10 parts by mole of an ethylene oxide adduct of bisphenol A. Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 80°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
- A reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of sebacic acid, 140 parts by mole of ethylene glycol and 10 parts by mole of an ethylene oxide adduct of bisphenol A. Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to give a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 80°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 3.
- A reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol and 10 parts by mole of an ethylene oxide adduct of bisphenol A. Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to provide a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 80°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film and provided in Table 3.
- The components listed in the table are as follows.
- TPA:
- terephthalic acid
- IPA:
- isophthalic acid
- SA:
- sebacic acid
- EG:
- ethylene glycol
- BPAE:
- ethylene oxide adduct of bisphenol A
- PTMG:
- polyoxytetramethylene glycol
- TMP:
- trimethylolpropane
- A reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of isophthalic acid, 150 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 10% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to provide a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 4.
- A reaction vessel was charged with 87 parts by mole of terephthalic acid, 13 parts by mole of isophthalic acid, 150 parts by mole of ethylene glycol, 3 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to provide a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 65°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 4.
- A reaction vessel was charged with 80 parts by mole of terephthalic acid, 15 parts by mole of isophthalic acid, 5 parts by mole of sebacic acid and 150 parts by mole of ethylene glycol. Antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to provide a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 75°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 4.
- A reaction vessel was charged with 95 parts by mole of terephthalic acid, 5 parts by mole of sebacic acid, 150 parts by mole of ethylene glycol and 20 parts by mole of neopentyl glycol. Trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component, and antimony trioxide and zinc acetate were added thereto as a polymerization catalyst in respective amounts of 450 ppm and 100 ppm each based on the whole acid component. Polymerization was conducted by direct polymerization to provide a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 75°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and shrinkage initiation temperature and the results of the evaluation of uneven shrinkage of the resultant film are provided in Table 4.
- The components listed in the table are as follows.
- TPA:
- terephthalic acid
- IPA:
- isophthalic acid
- ADA:
- adipic acid
- EG:
- ethylene glycol
- BPAE:
- ethylene oxide adduct of bisphenol A
- BPSE:
- ethylene oxide adduct of bisphenol S
- PTMG:
- polyoxytetramethylene glycol
- TMP:
- trimethylolpropane
- A reaction vessel was charged with 87 parts by mole of terephthalic acid, 13 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to provide a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 60°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40µm. The results of the measurement of the percentage shrinkage and the results of the evaluation of the solvent bondability and uneven shrinkage of the resultant film are provided in Table 5.
- A reaction vessel was charged with 90 parts by mole of terephthalic acid, 10 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 3 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to provide a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 60°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and the results of the evaluation of the solvent bondability and uneven shrinkage of the resultant film are provided in Table 5.
- A reaction vessel was charged with 75 parts by mole of terephthalic acid, 25 parts by mole of isophthalic acid, 140 parts by mole of ethylene glycol, 5 parts by mole of an ethylene oxide adduct of bisphenol A, 0.15 part by mole of trimethylolpropane and 7% by weight, based on the polymer, of polyoxytetramethylene glycol (molecular weight: 1000). Trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. Polymerization was conducted by direct polymerization to provide a polyester resin.
- The resultant polyester resin was melt-extruded at 270°C to prepare a raw film. The raw film was uniaxially stretched at 60°C by 3.8 times the original length in the direction of stretching (direction of TD) to give a heat shrinkable polyester film having a thickness of 40 µm. The results of the measurement of the percentage shrinkage and the results of the evaluation of the solvent bondability and uneven shrinkage of the resultant film are provided in Table 5.
- The components listed in the table are as follows.
- TPA:
- terephthalic acid
- IPA:
- isophthalic acid
- EG:
- ethylene glycol
- BPAE:
- ethylene oxide adduct of bisphenol A
- PTMG:
- polyoxytetramethylene glycol
- TMP:
- trimethylolpropane
- A reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 217 parts by mole of ethylene glycol and 3 parts by mole of an ethylene oxide adduct of bisphenol A. Zinc acetate was added thereto as a transesterification catalyst in an amount of 300 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C. After 91% of the theoretical amount of distilling of methanol was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 250 ppm based on the whole acid component, and germanium dioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to give a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- A reaction vessel was charged with 100 parts by mole of terephthalic acid, 145 parts by mole of ethylene glycol and 5 parts by mole of an ethylene oxide adduct of bisphenol A. Esterification was conducted by gradually raising the temperature of the reaction system to 260°C while pressurizing the reaction system with nitrogen. After 94% of the theoretical amount of distilling of water was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 100 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 350 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to give a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- A reaction vessel was charged with 100 parts by mole of terephthalic acid, 120 parts by mole of ethylene glycol and 10 parts by mole of an ethylene oxide adduct of bisphenol A. Esterification was conducted by gradually raising the temperature of the reaction system to 260°C while pressurizing the reaction system with nitrogen. After 92% of the theoretical amount of distilling of water was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid moiety, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 350 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to provide a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- A reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 190 parts by mole of ethylene glycol and 30 parts by mole of an ethylene oxide adduct of bisphenol A. Zinc acetate was added thereto as a transesterification catalyst in an amount of 300 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C. After 94% of the theoretical amount of distilling of methanol was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 250 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to give a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- A reaction vessel was charged with 100 parts by mole of terephthalic acid, 100 parts by mole of ethylene glycol and 50 parts by mole of an ethylene oxide adduct of bisphenol A. Esterification was conducted by gradually raising the temperature of the reaction system to 260°C while pressurizing the reaction system with nitrogen. After 92% of the theoretical amount of distilling of water was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 350 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to provide a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- A reaction vessel was charged with 100 parts by mole of methyl naphthalenedicarboxylate, 170 parts by mole of ethylene glycol and 65 parts by mole of an ethylene oxide adduct of bisphenol A. Zinc acetate was added thereto as a transesterification catalyst in an amount of 400 ppm based on the whole acid moiety, and transesterification was conducted while gradually raising the temperature of the system to 240°C. After 94% of the theoretical amount of distilling of methanol was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 300 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 500 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 4 hr to give a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- A reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 130 parts by mole of ethylene glycol and 85 parts by mole of an ethylene oxide adduct of bisphenol A. Zinc acetate was added thereto as a transesterification catalyst in an amount of 500 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C. After 94% of the theoretical amount of distilling of methanol was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 400 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 600 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 4 hr to give a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- A reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 120 parts by mole of ethylene glycol and 100 parts by mole of an ethylene oxide adduct of bisphenol A. Zinc acetate was added thereto as a transesterification catalyst in an amount of 500 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C. After 94% of the theoretical amount of distilling of methanol was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 400 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 600 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 4 hr to provide a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- A reaction vessel was charged with 100 parts by mole of terephthalic acid and 150 parts by mole of ethylene glycol. Esterification was conducted by gradually raising the temperature of the reaction system to 260°C while pressurizing the reaction system with nitrogen. After 92% of the theoretical amount of distilling of water was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 350 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to provide a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- A reaction vessel was charged with 70 parts by mole of dimethyl terephthalate, 30 parts by mole of dimethyl isophthalate and 220 parts by mole of ethylene glycol. Zinc acetate was added thereto as a transesterification catalyst in an amount of 300 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C. After 94% of the theoretical amount of distilling of methanol was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 250 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to provide a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- A reaction vessel was charged with 70 parts by mole of dimethyl terephthalate, 219 parts by mole of ethylene glycol and 1 part by mole of an ethylene oxide adduct of bisphenol A. Zinc acetate was added thereto as a transesterification catalyst in an amount of 300 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C. After 95% of the theoretical amount of distilling of methanol was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 250 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 450 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to give a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- A reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 100 parts by mole of ethylene glycol and 120 parts by mole of an ethylene oxide adduct of bisphenol A. Zinc acetate was added thereto as a transesterification catalyst in an amount of 600 ppm based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C. After 95% of the theoretical amount of distilling of methanol was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 450 ppm based on the whole acid component, and germanium dioxide was added thereto as a polymerization catalyst in an amount of 500 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to give a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- A reaction vessel was charged with 100 parts by mole of dimethyl terephthalate, 185 parts by mole of ethylene glycol and 35 parts by mole of cyclohexanedimethanol. Manganese acetate, cobalt acetate and titanium tetrabutoxide were added thereto as a transesterification catalyst in respective amounts of 200 ppm, 330 ppm and 400 ppm each based on the whole acid component, and transesterification was conducted while gradually raising the temperature of the system to 240°C. After 94% of the theoretical amount of distilling of methanol was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 400 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 4 hr to provide a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- A reaction vessel was charged with 100 parts by mole of terephthalic acid, 250 parts by mole of ethylene glycol and 10 parts by mole of an ethylene oxide adduct of bisphenol A. Esterification was conducted by gradually raising the temperature of the reaction system to 260°C while pressurizing the reaction system with nitrogen. After 92% of the theoretical amount of distilling of water was distilled off, trimethyl phosphate was added thereto as a stabilizer in an amount of 50 ppm based on the whole acid component, and antimony trioxide was added thereto as a polymerization catalyst in an amount of 350 ppm based on the whole acid component. The system was evacuated to 5 mmHg or less while gradually raising the temperature of the system to 280°C, and a reaction was allowed to proceed for about 3 hr to give a modified polyester resin. The resin composition and properties of the resultant modified polyester resin are provided in Table 6.
- The components listed in the table are as follows.
- TPA:
- terephthalic acid
- IPA:
- isophthalic acid
- NDCA:
- naphthalenedicarboxylic acid
- EG:
- ethylene glycol
- BPAE:
- ethylene oxide adduct of bisphenol A
- CHDM:
- cyclohexanedimethanol
- DEG:
- diethylene glycol
Claims (39)
- A polyester resin comprising units of a dicarboxylic acid component composed mainly of an aromatic dicarboxylic acid or its ester forming derivative and a diol component composed mainly of ethylene glycol and an ethylene oxide adduct of a bisphenol compound or its derivative, the content of the ethylene oxide adduct of a bisphenol compound or its derivative being 0.1 to 50% by mole based on the whole diol component, said resin further comprising 0.1 to 20% by weight of units of polyoxytetramethylene glycol and/or polyethylene glycol.
- A polyester resin according to claim 1, wherein the content of the polyoxytetramethylene glycol and/or polyethylene glycol units is 0.3 to 15% by weight.
- A polyester resin according to claim 1, wherein the polyoxytetramethylene glycol has a molecular weight of 300 to 4000.
- A polyester resin according to claim 1, wherein the polyethylene glycol has a molecular weight of 300 to 20000.
- A polyester resin according to claim 1, which further comprises 0.01 to 1% by weight of units of a tricarboxylic or higher polycarboxylic acid and/or a trihydric or higher polyhydric alcohol.
- A polyester resin according to claim 1, which further comprises 0.05 to 0.7% by weight of units of a tricarboxylic or higher polycarboxylic acid and/or a trihydric or higher polyhydric alcohol.
- A polyester resin according to claim 1, wherein the polycarboxylic acid is selected from trimellitic acid, pyromellitic acid and their anhydrides.
- A polyester resin according to claim 1, wherein the polyhydric alcohol is selected from trimethylolpropane, glycerin and pentaerythritol.
- A polyester resin according to claim 1, wherein the ethylene oxide adduct of a bisphenol compound is an ethylene oxide adduct of bisphenol A.
- A polyester resin according to claim 1, wherein the ethylene oxide adduct of a bisphenol compound is an ethylene oxide adduct of bisphenol S.
- A polyester resin according to claim 1, wherein the dicarboxylic acid component is composed mainly of tetephthalic acid and isophthalic acid or their ester forming derivative and the isophthalic acid or its ester forming derivative is contained in an amount of 7 to 30% by mole based on the whole dicarboxylic acid component.
- A polyester resin according to claim 11, wherein the isophthalic acid or its ester forming derivative is contained in an amount of 10 to 30% by mole based on the whole dicarboxylic acid component.
- A polyester resin according to claim 11, wherein the isophthalic acid or its ester forming derivative is contained in an amount of 12 to 30% by mole based on the whole dicarboxylic acid component.
- A polyester resin comprising units of a dicarboxylic acid component composed mainly of an aromatic dicarboxylic acid or its ester forming derivative and a diol component composed mainly of ethylene glycol and an ethylene oxide adduct of a bisphenol compound or its derivative, the content of the ethylene oxide adduct of a bisphenol compound or its derivative being 0.1 to 50% by mole based on the whole diol component, said resin further comprising 0.01 to 1% by weight of units of a tricarboxylic or higher polycarboxylic acid and/or a trihydric or higher polyhydric alcohol.
- A polyester resin according to claim 14, wherein the content of the tricarboxylic or higher polycarboxylic acid and/or trihydric or higher polyhydric alcohol units in the resin is 0.05 to 0.7% by weight.
- A polyester resin according to claim 14, wherein the polycarboxylic acid is selected from trimellitic acid, pyromellitic acid and their anhydrides.
- A polyester resin according to claim 14, wherein the polyhydric alcohol is selected from trimethylolpropane, glycerin and pentaerythritol.
- A polyester resin according to claim 14, wherein the content of the ethylene oxide adduct of a bisphenol compound or its derivative is 0.5 to 30% by mole based on the whole acid component.
- A polyester resin according to claim 14, wherein the ethylene oxide adduct of a bisphenol compound is an ethylene oxide adduct of bisphenol A.
- A polyester resin according to claim 14, wherein the ethylene oxide adduct of a bisphenol compound is an ethylene oxide adduct of bisphenol S.
- A polyester resin according to claim 14, wherein the dicarboxylic acid component is composed mainly of terephthalic acid and isophthalic acid or their ester forming derivative and the isophthalic acid or its ester forming derivative is contained in an amount of 7 to 30% by mole based on the whole dicarboxylic acid component.
- A polyester resin according to claim 14, wherein the isophthalic acid or its ester forming derivative is contained in an amount of 10 to 30% by mole based on the whole dicarboxylic acid component.
- A polyester resin according to claim 14, wherein the isophthalic acid or its ester forming derivative is contained in an amount of 12 to 30% by mole based on the whole dicarboxylic acid component.
- A polyester resin comprising units of an acid component composed mainly of terephthalic acid or its ester forming derivative and a diol component composed mainly of ethylene glycol and an ethylene oxide adduct of bisphenol A, the content of the ethylene oxide adduct of bisphenol A being 3 to 98% by mole based on the whole diol component, said polyester resin having an intrinsic viscosity of 0.5 to 1.4 dl/g and a diethylene glycol unit content of 1.2% by weight or less.
- A polyester resin according to claim 24, wherein the content of the ethylene oxide adduct of bisphenol A is 5 to 80% by mole based on the whole diol component.
- A polyester resin according to claim 24, wherein the content of the ethylene oxide adduct of bisphenol A is 10 to 60% by mole based on the whole diol component.
- A polyester resin according to claim 24, wherein the content of the ethylene oxide adduct of bisphenol A is 10 to 50% by mole based on the whole diol component.
- A polyester resin according to claim 24, wherein the intrinsic viscosity is 0.6 to 1.2 dl/g.
- A polyester resin according to claim 24, wherein the diethylene glycol unit content is 0.9% by weight or less.
- A polyester resin according to claim 24, wherein the diethylene glycol unit content is 0.8% by weight or less.
- A molded article of a polyester resin produced by molding a polyester resin according to any one of claims 1 to 30 through extrusion molding, blow molding, vacuum molding or injection molding.
- A polyester bottle for direct molding, comprising a polyester resin according to any one of claims 1 to 30.
- A heat shrinkable polyester film comprising a polyester resin according to any one of claims 1 to 30.
- A heat shrinkable polyester film according to claim 33, which exhibits a percentage shrinkage of 20% or more at 60°C in a unidirection when the film is heated in a hot water bath for 60 sec, and a shrinkage initiation temperature of 50°C or above.
- A heat shrinkable polyester film according to claim 34, which exhibits a percentage shrinkage of 25% or more at 60°C in a unidirection when the film is heated in a hot water bath for 60 sec.
- A heat shrinkable polyester film according to claim 34, which exhibits a percentage shrinkage of 30% or more at 60°C in a unidirection when the film is heated in a hot water bath for 60 sec.
- A heat shrinkable polyester film according to claim 34, which exhibits a percentage shrinkage of 1% or more at 50°C in a unidirection when the film is heated in a hot water bath for 60 sec.
- A heat shrinkable polyester film according to claim 34, which has a percentage shrinkage of 2% or more at 50°C in a unidirection when the film is heated in a hot water bath for 60 sec.
- A heat shrinkable polyester film according to claim 33, which exhibits an average shrinkage rate in the range of 0.3 to 3 %/sec in a period between 0 sec and 10 sec, between 10 sec and 20 sec and between 20 sec and 30 sec after the initiation of immersion of said film in a hot water bath.
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP96110824A EP0741161A3 (en) | 1991-08-28 | 1992-08-26 | Heat shrinkable polyester film |
EP96110825A EP0741166A3 (en) | 1991-08-28 | 1992-08-26 | Direct molded polyester bottle |
Applications Claiming Priority (20)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP217231/91 | 1991-08-28 | ||
JP21723191 | 1991-08-28 | ||
JP217232/91 | 1991-08-28 | ||
JP21723291 | 1991-08-28 | ||
JP4907/92 | 1992-01-14 | ||
JP490792A JPH05186579A (en) | 1992-01-14 | 1992-01-14 | Polyester resin for direct blow molding |
JP5290492A JPH0565338A (en) | 1991-07-11 | 1992-03-11 | Modified polyester resin |
JP52904/92 | 1992-03-11 | ||
JP11096392A JPH05305663A (en) | 1992-04-30 | 1992-04-30 | Heat-shrinkable polyester film |
JP110966/92 | 1992-04-30 | ||
JP11096592A JPH05261816A (en) | 1991-08-28 | 1992-04-30 | Heat-shrinkable polyester film |
JP11096492A JPH05305664A (en) | 1992-04-30 | 1992-04-30 | Heat-shrinkable polyester film |
JP11096692 | 1992-04-30 | ||
JP110963/92 | 1992-04-30 | ||
JP110964/92 | 1992-04-30 | ||
JP110967/92 | 1992-04-30 | ||
JP110965/92 | 1992-04-30 | ||
JP11096792 | 1992-04-30 | ||
JP4114890A JPH068322A (en) | 1991-08-28 | 1992-05-07 | Heat shrinkable polyester film |
JP114890/92 | 1992-05-07 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP96110825A Division EP0741166A3 (en) | 1991-08-28 | 1992-08-26 | Direct molded polyester bottle |
EP96110824A Division EP0741161A3 (en) | 1991-08-28 | 1992-08-26 | Heat shrinkable polyester film |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0532943A1 true EP0532943A1 (en) | 1993-03-24 |
EP0532943B1 EP0532943B1 (en) | 1998-06-10 |
Family
ID=27579527
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP19920114522 Expired - Lifetime EP0532943B1 (en) | 1991-08-28 | 1992-08-26 | Polyester resin |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP0532943B1 (en) |
DE (1) | DE69225855T2 (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0561596A2 (en) * | 1992-03-19 | 1993-09-22 | Teijin Limited | Oriented polyester film |
EP0826482A2 (en) * | 1996-08-30 | 1998-03-04 | Toyo Boseki Kabushiki Kaisha | Heat-shrinkable polyester films |
EP1055506A1 (en) * | 1999-05-21 | 2000-11-29 | Toyo Boseki Kabushiki Kaisha | Heat shrinkable polyester film |
US6630564B2 (en) * | 2001-09-26 | 2003-10-07 | Nan Ya Plastics Corporation | Copolyester with improved extrusion processing and color for extrusion blow molding |
WO2005052039A1 (en) * | 2003-11-21 | 2005-06-09 | Zimmer Ag | Method for producing pet films |
CN115613365A (en) * | 2022-11-14 | 2023-01-17 | 江苏动亦智能自动化科技有限公司 | Processing technology of high-temperature band seamless ring |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2402841A1 (en) * | 1974-01-22 | 1975-07-24 | Mehnert & Veeck Kg Lackfabrik | High-solid content hydroxy-polyester coating compsns - contg polyamides, derived from phenol hydroxy-alkyl ethers, and of low viscosity |
US4067835A (en) * | 1975-12-23 | 1978-01-10 | Kao Soap Co., Ltd. | Glass fiber sizing agent |
EP0271928A2 (en) * | 1986-12-19 | 1988-06-22 | Toyo Boseki Kabushiki Kaisha | Thermo-shrinkable polyester film |
EP0371824A2 (en) * | 1988-12-01 | 1990-06-06 | Mitsubishi Rayon Co., Ltd. | Toner |
EP0372424A2 (en) * | 1988-12-07 | 1990-06-13 | Diafoil Hoechst Co., Ltd | Shrinkable copolyester film |
-
1992
- 1992-08-26 EP EP19920114522 patent/EP0532943B1/en not_active Expired - Lifetime
- 1992-08-26 DE DE1992625855 patent/DE69225855T2/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2402841A1 (en) * | 1974-01-22 | 1975-07-24 | Mehnert & Veeck Kg Lackfabrik | High-solid content hydroxy-polyester coating compsns - contg polyamides, derived from phenol hydroxy-alkyl ethers, and of low viscosity |
US4067835A (en) * | 1975-12-23 | 1978-01-10 | Kao Soap Co., Ltd. | Glass fiber sizing agent |
EP0271928A2 (en) * | 1986-12-19 | 1988-06-22 | Toyo Boseki Kabushiki Kaisha | Thermo-shrinkable polyester film |
EP0371824A2 (en) * | 1988-12-01 | 1990-06-06 | Mitsubishi Rayon Co., Ltd. | Toner |
EP0372424A2 (en) * | 1988-12-07 | 1990-06-13 | Diafoil Hoechst Co., Ltd | Shrinkable copolyester film |
Cited By (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0561596A2 (en) * | 1992-03-19 | 1993-09-22 | Teijin Limited | Oriented polyester film |
EP0561596A3 (en) * | 1992-03-19 | 1994-08-31 | Teijin Ltd | |
EP0787760A2 (en) * | 1992-03-19 | 1997-08-06 | Teijin Limited | Oriented polyester film |
EP0787760A3 (en) * | 1992-03-19 | 1998-04-01 | Teijin Limited | Oriented polyester film |
EP0826482A2 (en) * | 1996-08-30 | 1998-03-04 | Toyo Boseki Kabushiki Kaisha | Heat-shrinkable polyester films |
EP0826482A3 (en) * | 1996-08-30 | 1998-06-10 | Toyo Boseki Kabushiki Kaisha | Heat-shrinkable polyester films |
US5932685A (en) * | 1996-08-30 | 1999-08-03 | Toyo Boseki Kabushiki Kaisha | Heat-shrinkable polyester films |
US6451445B1 (en) | 1999-05-21 | 2002-09-17 | Toyo Boseki Kabushiki Kaisha | Heat shrinkable polyester film |
EP1055506A1 (en) * | 1999-05-21 | 2000-11-29 | Toyo Boseki Kabushiki Kaisha | Heat shrinkable polyester film |
EP1595691A2 (en) * | 1999-05-21 | 2005-11-16 | Toyo Boseki Kabushiki Kaisha | Heat shrinkable polyester film |
USRE40274E1 (en) | 1999-05-21 | 2008-04-29 | Toyo Boseki Kabushiki Kaisha | Heat shrinkable polyester film |
EP1595691A3 (en) * | 1999-05-21 | 2010-09-29 | Toyo Boseki Kabushiki Kaisha | Heat shrinkable polyester film |
US6630564B2 (en) * | 2001-09-26 | 2003-10-07 | Nan Ya Plastics Corporation | Copolyester with improved extrusion processing and color for extrusion blow molding |
WO2005052039A1 (en) * | 2003-11-21 | 2005-06-09 | Zimmer Ag | Method for producing pet films |
CN100334141C (en) * | 2003-11-21 | 2007-08-29 | 齐默尔股份公司 | Method for producing PET films |
EA010657B1 (en) * | 2003-11-21 | 2008-10-30 | Лурги Циммер Гмбх | Method for producing pet films and films |
CN115613365A (en) * | 2022-11-14 | 2023-01-17 | 江苏动亦智能自动化科技有限公司 | Processing technology of high-temperature band seamless ring |
Also Published As
Publication number | Publication date |
---|---|
EP0532943B1 (en) | 1998-06-10 |
DE69225855D1 (en) | 1998-07-16 |
DE69225855T2 (en) | 1998-11-12 |
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